CN1958619A - Adduct of round magnesium halides, preparation method and application - Google Patents
Adduct of round magnesium halides, preparation method and application Download PDFInfo
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Abstract
This invention provides a magnesium halide adduct, whose chemical formula is MgX2-mROH-nE, where X is Cl or Br; R is C1-C12 alkyl, C3-C10 cycloalkyl or C6-C10 aryl; m is 1-5; n is 0.005-0.5; E is diol ester compound shown in formula I. The particle sizes of the magnesium halide adduct are easy to control, and the particle size distribution is narrow. The catalyst using the magnesium halide adduct as the carrier has a uniform active center distribution. When the catalyst is used for propylene polymerization, the fine powder of the polymer is obvious reduced. The catalyst shows high catalytic activity and steric regularity.
Description
Technical field
The present invention relates to a kind of adduct of magnesium halides and its production and application.More particularly, relate to the spherical adduct of a kind of magnesium halide, pure and mild ester ternary component, and the application of this adducts in the preparation olefin polymerization catalysis.
Technical background
Magnesium halide/alcohol adducts with and be known in the art as carrier being applied in olefin polymerization catalysis preparation.Obtain spherical catalyst after this adducts and halogenated titanium and the reaction of electron donor compound, be used for olefinic polymerization particularly during propylene polymerization, have very high polymerization activity and taxis, resulting polymkeric substance also has good particle form and higher apparent density.
Disclosed adduct of magnesium halides is the alcohol adduct of magnesium chloride mostly, generally includes magnesium chloride and pure binary composition.Also comprise a spot of water in some disclosed alcohol adduct.This type of alcohol adduct can be extruded or the preparation of method such as high-speed stirring by spraying drying, spray cooling, high pressure.As: the disclosed magnesium chloride alcohol adduct of US4421674, US4469648, WO8707620, WO9311166, US5100849, US6020279, US4399054, EP0395383, US6127304 and US6323152.
When the catalyzer by this class magnesium chloride alcohol adduct preparation is used for olefinic polymerization, is easy to take place the broken phenomenon of polymkeric substance, thereby causes fine polymer powder more.Its major cause may be because in adducts and halogenated titanium and the electron donor compound reaction process, and the catalyst active center that forms on the adducts carrier is inhomogeneous to cause.In order to overcome this shortcoming, people attempt again the electron donor compound is introduced in the preparing carriers of magnesium chloride alcohol adduct in advance, for example: in Chinese patent ZL02136543.1 and CN1563112A technology, known internal electron donor of the industry such as phthalate compound were introduced in synthesizing of carrier, form the spherical carrier of " magnesium dichloride-alcohol-phthalic ester " mixture, then this carrier and titanium tetrachloride reaction are formed catalyzer.But because the spherical carrier of described mixture is clamminess in preparation process easily, be difficult to form the suitable spheroidal particle of size, its disclosed ball type carrier is of a size of D50:70-200, and the catalytic activity that is used for propylene polymerization only is 406gPP/gcat, and is therefore also unsatisfactory.
Therefore, being starved of provides a kind of new adduct of magnesium halides particle, and it is the particulate narrower particle size distribution not only, and particle diameter is controlled easily, and the preparation method is simple and easy to do, is very beneficial for suitability for industrialized production.Simultaneously, also has excellent comprehensive performances by its prepared olefin polymerization catalysis.
Summary of the invention
The invention provides a kind of adduct of magnesium halides, it is the spherical adduct that contains magnesium halide, pure and mild ester ternary component, and uniform particles is easy to control, and size distribution is narrower.With the catalyzer of this adducts,, advantages of high catalytic activity and taxis have been shown being used for olefinic polymerization particularly during propylene polymerization as preparing carriers.
A kind of adduct of magnesium halides is as formula M gX
2Shown in-the mROH-nE, X is a chlorine or bromine in the formula, and R is C
1-C
12Alkyl, C
3-C
10Cycloalkyl or C
6-C
10Aryl, E are the diol ester compound shown in the general formula (I):
R in the general formula (I)
1-R
6Can be identical or inequality, be hydrogen or C
1-C
10The alkyl of straight or branched, C
3-C
10Cycloalkyl, C
6-C
10Aryl, C
7-C
10Alkaryl or aralkyl; R
1-R
6In two or more groups mutually bonding generate one or several condensed ring structure; R
7And R
8Can be identical or inequality, represent C
1-C
10Straight or branched alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aryl, the benzene ring hydrogen can randomly be replaced by halogen atom in described aryl or alkaryl or the aryl;
Wherein m is 1-5, preferred 1.5-3.5; N is 0.005-0.5, preferred 0.02-0.3.
Above-mentioned formula M gX
2Among-the mROH-nE, described magnesium halide MgX
2In, X is a chlorine or bromine, is preferably chlorine.Described X also can be by C
1～C
14Alkyl or aryl, alkoxyl group or aryloxy replace.Concrete compound is as magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium etc., wherein preferred magnesium dichloride.Described halogenated magnesium compound can be used alone or as a mixture.
Described alcohol roh, wherein R is C
1-C
12Alkyl, C
3-C
10Cycloalkyl or C
6-C
10Aryl, preferred R is C
1-C
4Alkyl.Concrete compound is methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, n-hexyl alcohol n-Octanol, 2-Ethylhexyl Alcohol, ethylene glycol or propylene glycol.
Described ester E is the diol ester compound shown in the general formula (I), in the diol ester compound of above-mentioned general formula (I), and preferred R
1, R
2, R
5, R
6Be not the compound of hydrogen simultaneously; More preferably R wherein
1, R
2, R
5, R
6In to have a group at least be the compound of hydrogen; Further preferred R
1And R
2, R
5And R
6In a group is arranged respectively is hydrogen, and another group is methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, phenyl or halogenated phenyl etc.
In the diol ester compound of above-mentioned general formula (I), preferred R
7And R
8Group is selected from methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, amyl group, cyclopentyl, cyclohexyl, phenyl, halogenated phenyl, aminomethyl phenyl, halogenated aminomethyl phenyl, indenyl, benzyl or phenylethyl.More preferably, R
7And R
8Group is selected from phenyl, halogenated phenyl, aminomethyl phenyl or halogenated aminomethyl phenyl.
Suitable diol ester compound comprises:
1, the ammediol dibenzoate, the 2-methyl isophthalic acid, the ammediol dibenzoate, 2-ethyl-1, the ammediol dibenzoate, the 2 dibenzoate, (R)-1-phenyl-1, the ammediol dibenzoate, 1,3-phenylbenzene-1, ammediol dibenzoate, 1,3-phenylbenzene-1, ammediol two n Propanoic acid esters, 1,3-phenylbenzene-2-methyl isophthalic acid, the ammediol dipropionate, 1,3-phenylbenzene-2-methyl isophthalic acid, ammediol diacetate esters, 1,3-phenylbenzene-2 dibenzoate, 1,3-phenylbenzene-2 dipropionate, 1,3-di-t-butyl-2-ethyl-1, the ammediol dibenzoate, 1,3-phenylbenzene-1, the ammediol diacetate esters, 1,3-di-isopropyl-1,3-propyl alcohol two (4-butylbenzoic acid) ester, 1-phenyl-2-amino-1,3 propylene glycol dibenzoates, 1-phenyl-2-methyl isophthalic acid, 3-butyleneglycol dibenzoate, phenyl-2-methyl isophthalic acid, 3-butyleneglycol two pivalates, 3-butyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol dibenzoate, (2S, 4S)-(+)-2,4-pentanediol dibenzoate, (2R, 4R)-(+)-2,4-pentanediol dibenzoate, 2,4-pentanediol two (Chlorodracylic acid) ester, 2,4-pentanediol two (m-chlorobenzoic acid) ester, 2,4-pentanediol two (parabromobenzoic acid) ester, 2,4-pentanediol two (o-bromobenzoic acid) ester, 2,4-pentanediol two (p-methylbenzoic acid) ester, 2,4-pentanediol two (p-tert-butyl benzoic acid) ester, 2,4-pentanediol two (to butylbenzoic acid) ester, the 2-methyl isophthalic acid, 3-pentanediol two (Chlorodracylic acid) ester, the 2-methyl isophthalic acid, 3-pentanediol two (p-methylbenzoic acid) ester, 2-butyl-1,3-pentanediol two (p-methylbenzoic acid) ester, the 2-methyl isophthalic acid, 3-pentanediol two (p-tert-butyl benzoic acid) ester, the 2-methyl isophthalic acid, 3-pentanediol pivalate, the 2-methyl isophthalic acid, 3-pentanediol phenylformic acid laurate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol phenylformic acid laurate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2-allyl group-1,3-pentanediol dibenzoate, the 2-methyl isophthalic acid, 3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-propyl group-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 1,3-pentanediol two (Chlorodracylic acid) ester, 1,3-pentanediol two (m-chlorobenzoic acid) ester, 1,3-pentanediol two (parabromobenzoic acid) ester, 1,3-pentanediol two (o-bromobenzoic acid) ester, 1,3-pentanediol two (p-methylbenzoic acid) ester, 1,3-pentanediol two (p-tert-butyl benzoic acid) ester, 1,3-pentanediol two (to butylbenzoic acid) ester, 1,3-pentanediol phenylformic acid laurate, 1,3-pentanediol two laurates, 1,3-pentanediol dipropionate, the 2-methyl isophthalic acid, 3-pentanediol phenylformic acid laurate, 2,, 2-dimethyl-1,3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol phenylformic acid laurate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2-allyl group-1,3-pentanediol dibenzoate, the 2-methyl isophthalic acid, 3-pentanediol phenylformic acid laurate, 2,2,4-trimethylammonium-1,3-pentanediol di-isopropyl manthanoate, 1-trifluoromethyl-3-methyl-2,4-pentanediol dibenzoate, 2, two pairs of fluoro methyl benzoic acid esters of 4-pentanediol, 2,4-pentanediol two (2-furancarboxylic acid) ester, 2-methyl-6-heptene-2,4-heptanediol dibenzoate, 3-methyl-6-heptene-2,4-heptanediol dibenzoate, 4-methyl-6-heptene-2,4-heptanediol dibenzoate, 5-methyl-6-heptene-2,4-heptanediol dibenzoate, 6-methyl-6-heptene-2,4-heptanediol dibenzoate, 3-ethyl-6-heptene-2,4-heptanediol dibenzoate, 4-ethyl-6-heptene-2,4-heptanediol dibenzoate, 5-ethyl-6-heptene-2,4-heptanediol dibenzoate, 6-ethyl-6-heptene-2,4-heptanediol dibenzoate, 3-propyl group-6-heptene-2,4-heptanediol dibenzoate, 4-propyl group-6-heptene-2,4-heptanediol dibenzoate, 5-propyl group-6-heptene-2,4-heptanediol dibenzoate, 6-propyl group-6-heptene-2,4-heptanediol dibenzoate, 3-butyl-6-heptene-2,4-heptanediol dibenzoate, 4-butyl-6-heptene-2,4-heptanediol dibenzoate, 5-butyl-6-heptene-2,4-heptanediol dibenzoate, 6-butyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dimethyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-diethyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dipropyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dibutyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dimethyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-diethyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dipropyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dibutyl-6-heptene-2,4-heptanediol dibenzoate, 3-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 5-ethyl-3,5-heptanediol dibenzoate, 3-propyl group-3,5-heptanediol dibenzoate, 4-propyl group-3,5-heptanediol dibenzoate, 3-butyl-3,5-heptanediol dibenzoate, 2,3-dimethyl-3,5-heptanediol dibenzoate, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,5-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 3,3-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 4,5-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-3-ethyl-3,5-heptanediol dibenzoate, 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-5-ethyl-3,5-heptanediol dibenzoate, 3-methyl-3-ethyl-3,5-heptanediol dibenzoate, 3-methyl-4-ethyl-3,5-heptanediol dibenzoate, 3-methyl-5-ethyl-3,5-heptanediol dibenzoate, 4-methyl-3-ethyl-3,5-heptanediol dibenzoate, 4-methyl-4-ethyl-3,5-heptanediol dibenzoate etc.
In the diol ester compound of general formula (I), R
1-R
6In two or more groups mutually bonding generate one or several condensed ring structure, the compound of preferred formula (II) expression wherein:
In the general formula (II), R
1, R
2, R
5And R
6Identical or inequality, be hydrogen or C
1-C
10The alkyl of straight or branched, C
3-C
10Cycloalkyl, C
6-C
10Aryl, C
7-C
10Alkaryl or aralkyl; R
7And R
8As the definition in the general formula (I), R ' is the C of hydrogen identical or inequality, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aralkyl.
Suitable examples of compounds comprises:
9, two (benzoyloxy methyl) fluorenes, 9 of 9-, two ((meta-methoxy benzoyloxy) methyl) fluorenes, 9 of 9-, two ((m-chloro benzoyloxy) methyl) fluorenes, 9 of 9-, two ((to the chlorobenzene carboxyphenyl) methyl) fluorenes, 9 of 9-, two (the Chinese cassia tree carboxyl methyl) fluorenes of 9-, 9-(benzoyloxy methyl)-9-(the third carboxyl methyl) fluorenes, 9, two (the third carboxyl methyl) fluorenes, 9 of 9-, two (the propylene carboxyl methyl) fluorenes, 9 of 9-, two (neo-pentyl carboxyl methyl) fluorenes of 9-etc.
Above-mentioned diol-lipid compound is disclosed among Chinese patent CN1453298A, CN1436796A and PCT/CN03/00110 and the PCT/CN03/00111, and its associated viscera is incorporated herein the present invention as a reference.
One of adduct of magnesium halides of the present invention more preferably embodiment is described MgX
2Among-the mROH-nE, X is that chlorine, R are C
1-C
4Alkyl, m be 1.5-3.5, n is 0.02-0.3.
Adduct of magnesium halides of the present invention can adopt the method preparation of the known magnesium halide alcohol adduct of the industry, for example can extrude or method such as high-speed stirring by spraying drying, spray cooling, high pressure.Usually, earlier with contact reacts under the condition of magnesium halide, the heating of pure and mild ester three components, final temperature of reaction will reach and can make magnesium halide, the fusing of pure and mild ester adducts form melt, is preferably 100 ℃～130 ℃, further solidify to form solid particulate then in inert media.Described inert media generally adopts liquid aliphatic hydro carbons inert solvent, as kerosene, paraffin oil, vaseline oil, white oil etc., when needing, also can randomly add some silicoorganic compound or tensio-active agent, as methyl-silicone oil etc.When the contact reacts of magnesium halide, pure and mild ester three components, also can randomly add above-mentioned inert liquid medium.
A kind of preparation method of adduct of magnesium halides of the present invention, it comprises following steps:
1. the preparation of adduct of magnesium halides melt
In airtight reactor,, under agitation mixture heating up is warmed up to 100-130 ℃, to forming the adduct of magnesium halides melt with magnesium halide, alcohol, diol ester and randomly inert media mixing.
The add-on of magnesium halide is 0.1～1.0mol/L liquid medium, and the add-on of pure and mild diol ester is respectively in every mole of magnesium: 1～5 and 0.005～0.5.
2. spherical adduct of magnesium halides particulate forms
Above-mentioned adduct of magnesium halides melt is put into the refrigerative inert media after high shear forces, form spherical adduct of magnesium halides particle.High shear forces can adopt conventional method, as high-speed mixing method (as Chinese patent CN 1330086), and spray method (as US6020279) and high-gravity rotating bed (as CN1580136A) and mulser (CN1463990A) etc.
Heat-eliminating medium can adopt the lower inert hydrocarbon solvent of boiling point, as pentane, hexane, heptane, gasoline or petrol ether etc.With before material contacts, the temperature of heat-eliminating medium is controlled at-20 ℃～-40 ℃.
The above-mentioned spherical adduct of magnesium halides particle that obtains can be used for preparing the catalyzer of olefinic polymerization after inert hydrocarbon solvent washing, drying.
Can adopt known synthetic method for the synthetic of catalyzer, as with as described in the adduct of magnesium halides particle directly with the halogenated titanium reaction, do not need to add again the catalyzer that the internal electron donor compound can obtain excellent property usually.But the needs according to practical application also can randomly add the known internal electron donor compound of some industry.
It is worthy of note, the spherical adduct of magnesium halide of the present invention, pure and mild ester ternary component, uniform particles is easy to control, and size distribution is narrower.With the catalyzer of this adducts as preparing carriers, the active centre distribution uniform is being used for olefinic polymerization particularly during propylene polymerization, and the fine powder of polymkeric substance (fragmentation) obviously reduces.Simultaneously, advantages of high catalytic activity and taxis have been shown.
Embodiment
Following Example is used for illustrating the present invention, is not to be used for limiting the scope of the invention.
Testing method:
1, melt index: measure according to ASTM D1238-99.
2, polymkeric substance degree of isotacticity: adopt the heptane extraction process to measure (heptane boiling extracting 6 hours): two gram exsiccant polymer samples, be placed in the extractor with the extracting of boiling heptane after 6 hours, the polymer weight (g) that residuum is dried to the constant weight gained is degree of isotacticity with 2 ratio.
3, size distribution test: adduct of magnesium halides particulate median size and size-grade distribution MastersSizer 2000 (manufacturing) particle size analyzer determination by Malvern Instruments Ltd.
The synthetic method of diol ester compound is with reference to Chinese patent CN1453298A among the embodiment.
Embodiment 1
In the autoclave of 1L, add white oil 9ml, 180ml silicone oil, 15 gram magnesium chloride, 28ml ethanol and 5ml 2,4-pentanediol dibenzoate, under agitation be warmed up to 125 ℃, stirred 3 hours down, mixture is put in advance the 3L hexane that is cooled to-30 ℃ at 125 ℃, elimination liquid, with hexane wash solid three times, vacuum-drying, obtain the spherical magnesium chloride adductss of 31 grams.
Test result such as table 1.
Embodiment 2
Remove 10ml 2, outside the 4-pentanediol dibenzoate, with embodiment 1.Test result such as table 1.
Embodiment 3
Remove 15ml 2, outside the 4-pentanediol dibenzoate, with embodiment 1.Test result such as table 1.
Embodiment 4
Remove 20ml 2, outside the 4-pentanediol dibenzoate, with embodiment 1.Test result such as table 1.
Embodiment 5
Remove with 15ml 4-ethyl 3, the 5-heptanediol replaces 5ml 2, outside the 4-pentanediol dibenzoate, with embodiment 1.Test result such as table 1.
Comparative Examples 1
Except that not adding 2,4-pentanediol dibenzoate is outer with embodiment 1.Test result such as table 1.
Comparative Examples 2
Remove with 10ml n-butyl phthalate replacement 5ML 2, outside the 4-pentanediol dibenzoate, with embodiment 1.The magnesium chloride adducts that obtains is clamminess.
Embodiment 6
A. spherical catalyst is synthetic
In the glass reaction bottle of 300ML, add the titanium tetrachloride of 100ml, be cooled to-20 ℃, add spherical magnesium chloride adducts 8 grams of embodiment 4, be warming up to 100 ℃, elimination liquid, wash secondary with titanium tetrachloride, use hexane wash three times, obtain spherical catalyst after the vacuum-drying.
B. propylene polymerization
In the 5L autoclave, add propylene 2.5L, triethyl aluminum 1mmol, CHMMS0.05mmol, spherical catalyst 10mg, hydrogen 1.5L (standard volume) is warmed up to 70 ℃, polymerization 1 hour.Test result such as table 2,3.
Embodiment 7
Except that the spherical magnesium chloride adducts with embodiment 5 replaces the spherical magnesium chloride adducts of embodiment 4, with embodiment 6.Test result such as table 2,3.
Comparative Examples 3
A. spherical catalyst is synthetic
In the glass reaction bottle of 300ML, the titanium tetrachloride that adds 100ML, be cooled to-20 ℃, add spherical magnesium chloride adducts 8 grams of Comparative Examples 1, be warming up to 100 ℃, in temperature-rise period, add DIBP1.5ML, elimination liquid, wash secondary with titanium tetrachloride, use hexane wash three times, obtain spherical catalyst after the vacuum-drying.
B. propylene polymerization
With embodiment 6.Test result such as table 2,3.
Table 1 magnesium chloride adducts
| Embodiment | Diol ester content, wt% | Alcohol/magnesium mol/mol | D50 | (D90-D10) /D50 |
| Embodiment 1 | 2.3 | 2.65 | 40.2 | 1.6 |
| Embodiment 2 | 5.6 | 2.57 | 51.4 | 1.7 |
| Embodiment 3 | 7.4 | 2.50 | 47.0 | 1.6 |
| Embodiment 4 | 10.3 | 1.86 | 57.1 | 1.4 |
| Embodiment 5 | 2.8 | 2.25 | 42.4 | / |
| Comparative Examples 1 | 0 | 2.70 | 35.0 | / |
| Comparative Examples 2 | The magnesium chloride adducts is clamminess | |||
Table 2 is by the catalyzer of magnesium chloride adducts preparation
| Embodiment | Polymerization activity kgPP/gcat | Polymkeric substance I.I % | Polymkeric substance MI g/ml | Polymer B .D g/ml |
| Embodiment 6 | 47 | 96.2 | 1.1 | 0.46 |
| Embodiment 7 | 34 | 96.9 | 7.7 | 0.46 |
| Comparative Examples 3 | 29 | 97.4 | 6.4 | 0.45 |
The size distribution of table 3 polymkeric substance
| Embodiment | The above wt% of 10 orders | 10-20 order wt% | 20-40 order wt% | 40-60 order wt% | 60 following wt% |
| Embodiment 6 | 45.6 | 38.1 | 10.9 | 3.7 | 1.7 |
| Embodiment 7 | 42.0 | 41.5 | 13.3 | 1.7 | 1.6 |
| Comparative Examples 3 | 10.0 | 37.3 | 42.1 | 4.5 | 6.6 |
More as can be seen, be used for propylene polymerization by the prepared catalyzer of magnesium chloride adduction of the present invention and shown advantages of high catalytic activity by the data of last table, gained polymeric fine powder is less simultaneously, illustrate polymkeric substance broken phenomenon obviously reduce.
Claims (11)
1, a kind of adduct of magnesium halides is as MgX
2Shown in-the mROH-nE, X is a chlorine or bromine in the formula, and R is C
1-C
12Alkyl, C
3-C
10Cycloalkyl or C
6-C
10Aryl, m is 1-5, n is 0.005-0.5, E is the diol ester compound shown in the general formula (I):
R in the general formula (I)
1-R
6Can be identical or inequality, be hydrogen or C
1-C
10The alkyl of straight or branched, C
3-C
10Cycloalkyl, C
6-C
10Aryl, C
7-C
10Alkaryl or aralkyl; R
1-R
6In two or more groups mutually bonding generate one or several condensed ring structure; R
7And R
8Can be identical or inequality, represent C
1-C
10Straight or branched alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aryl, the benzene ring hydrogen can randomly be replaced by halogen atom in described aryl or alkaryl or the aryl.
2, adduct of magnesium halides according to claim 1, described MgX
2Among-the mROH-nE, R is C
1-C
4Alkyl.
3, adduct of magnesium halides according to claim 1, in the diol ester compound of wherein said general formula (I), R
1, R
2, R
5, R
6Be not hydrogen simultaneously.
4, adduct of magnesium halides according to claim 3, in the diol ester compound of wherein said general formula (I), R
1, R
2, R
5, R
6In to have a group at least be hydrogen.
5, adduct of magnesium halides according to claim 1, in the diol ester compound of wherein said general formula (I), R
1And R
2, R
5And R
6In a group is arranged respectively is hydrogen, and another group is methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, phenyl or halogenated phenyl.
6, adduct of magnesium halides according to claim 1, in the diol ester compound of wherein said general formula (I), R
7And R
8Identical or different, be selected from methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, amyl group, cyclopentyl, cyclohexyl, phenyl, halogenated phenyl, aminomethyl phenyl, halogenated aminomethyl phenyl, indenyl, benzyl or phenylethyl.
7, adduct of magnesium halides according to claim 1, the diol ester compound of wherein said general formula (I) comprises the compound of general formula (II):
Wherein, R
1And R
2, R
5-R
8As the definition in the general formula (I), R ' is the C of hydrogen identical or inequality, halogen atom, straight or branched
1-C
20Alkyl, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aralkyl.
8, adduct of magnesium halides according to claim 1, wherein m is 1.5-3.5, n is 0.02-0.3.
9, adduct of magnesium halides according to claim 1, described MgX
2Among-the mROH-nE, X is that chlorine, R are C
1-C
4Alkyl, m be 1.5-3.5, n is 0.02-0.3.
10, the preparation method of the described adduct of magnesium halides of claim 1, it comprises following steps:
(1) preparation of adduct of magnesium halides melt
In airtight reactor, magnesium halide, alcohol, diol ester and liquid medium are mixed, under agitation mixture heating up is warmed up to 100-130 ℃, to forming the adduct of magnesium halides melt, wherein the add-on of magnesium halide is 0.1～1.0mol/L liquid medium, and the add-on of pure and mild diol ester is respectively in every mole of magnesium: 1～5 and 0.005～0.5;
(2) the adduct of magnesium halides particulate forms
Above-mentioned adduct of magnesium halides melt is put into heat-eliminating medium after high shear forces, form spherical adduct of magnesium halides particle, the temperature of heat-eliminating medium is controlled at-20 ℃～-40 ℃.
11, the application of the described adduct of magnesium halides of one of claim 1-9 in the preparation olefin polymerization catalysis.
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| CN101906017A (en) * | 2009-06-04 | 2010-12-08 | 中国石油化工股份有限公司 | Method for preparing alkoxyl magnesium solid particles |
| CN102796211A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method thereof, catalyst for olefin polymerization, and olefin polymerization method |
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| CN1213080C (en) * | 2003-04-21 | 2005-08-03 | 中国石油化工股份有限公司 | Catalyst for olefine polymerizing reaction and its components |
| CN1310963C (en) * | 2003-05-30 | 2007-04-18 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization reaction and catalyst |
| CN1286863C (en) * | 2004-03-25 | 2006-11-29 | 浙江大学 | Olefinic polymerization catalyst carried by carrier of sphere MgCl-alcohol-organic complexing agent and preparation method |
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| CN101906017A (en) * | 2009-06-04 | 2010-12-08 | 中国石油化工股份有限公司 | Method for preparing alkoxyl magnesium solid particles |
| CN102796211A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method thereof, catalyst for olefin polymerization, and olefin polymerization method |
| CN102796211B (en) * | 2011-05-27 | 2014-03-12 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method thereof, catalyst for olefin polymerization, and olefin polymerization method |
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