CN101486722A - Magnesium halide adduct, preparation and use thereof - Google Patents
Magnesium halide adduct, preparation and use thereof Download PDFInfo
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Abstract
The invention provides a magnesium halide addition compound shown as general formula MgX2-mROH-nE-pH2O, wherein, X refers to chlorine or bromine, R refers to the alkyl of C1-C12; naphthene base of C3-C10 or the aryl of the C6-C10; E refers to o-alkoxybenzoic ether compound shown in the general formula (II); m ranges from 1 to 5; n ranges from 0.005 to 1.0; and P ranges from 0 to 0.8.
Description
Technical field
The present invention relates to a kind of adduct of magnesium halides and its production and application.Specifically, relate to the spherical adduct of a kind of magnesium halide, pure and mild o-alkoxyl benzoic ether 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.
Chinese patent CN101050245A discloses a kind of new adduct of magnesium halides ball type carrier, and it is as formula M gX
2-mROH-nE-pH
2Shown in the O, wherein said E is C, C-two-oxyl hydrocarbon compounds.The narrower particle size distribution of this carrier granule, particle diameter is controlled easily.Simultaneously, have better hydrogen regulation sensitivity by its prepared olefin polymerization catalysis, the particle form of resulting polymers is better.But described catalyzer is under high hydrogen concentration during polypropylene, and its upright structure orientation property, particularly the degree of isotacticity of polymkeric substance is on the low side during high fusion index, awaits further to improve.
Therefore, the over-all properties that the preparation that provides a kind of new adduct of magnesium halides ball type carrier to be used for the polyolefine spherical catalyst improves catalyzer is provided, particularly to improve the degree of isotacticity of polymkeric substance when high fusion index, so that directly synthetic high fusion index, high normal propene polymer in polymerization reactor, this polymkeric substance not only mechanical property is good, and has good processing characteristics.
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 o-alkoxyl benzoic ether ternary component.Being used for olefinic polymerization particularly during propylene polymerization, can obtain the propene polymer of high fusion index, high taxis.
A kind of adduct of magnesium halides is shown in general formula (I).
MgX
2-mROH-nE-pH
2O
(I)
In the general formula (I), X is a chlorine or bromine, and R is C
1-C
12Alkyl, C
3-C
10Cycloalkyl or C
6-C
10Aryl, E are the o-alkoxyl benzoate compounds shown in the general formula (II):
In the general formula (II), R
1And R
2Identical or different, be C
1-C
12The alkyl of straight or branched, C
3-C
10Cycloalkyl or C
6-C
10Aryl, C
7-C
10Alkaryl or aralkyl; R
1, R
2With R can be identical or different;
In the general formula (I), m is 1.0-5.0; N is 0.005-1.0; P is 0-0.8.
At the magnesium halide MgX described in the general formula (I)
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.
In the alcohol roh described in the general formula (I), R is C
1-C
12Alkyl, C
3-C
10Cycloalkyl or C
6-C
10Aryl, preferred R is C
1-C
4Alkyl.Concrete compound can be 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.
In general formula (II), R
1Or R
2Can be identical or different, be C
1-C
12The alkyl of straight or branched, C
3-C
10Cycloalkyl or C
6-C
10Aryl, C
7-C
10Alkaryl or aralkyl.Concrete as: methyl, ethyl, n-propyl, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, base, isopentyl, cyclopentyl, cyclohexyl, phenyl, aminomethyl phenyl, indenyl, benzyl or phenylethyl etc.Preferably, R
1Or R
2Be selected from C
1-C
6The alkyl of straight or branched, C
3-C
6Cycloalkyl or C
6-C
10Aryl.
More preferably, R
1And R
2Group is selected from methyl, ethyl, propyl group, butyl, sec.-propyl.
The particular compound of the o-alkoxyl benzoates shown in the general formula (II) is as the o-methoxybenzoic acid methyl esters, the o-methoxybenzoic acid ethyl ester, the o-methoxybenzoic acid n-propyl, the o-methoxybenzoic acid isopropyl ester, the positive butyl ester of o-methoxybenzoic acid, the o-methoxybenzoic acid isobutyl ester, the o-ethoxybenzoic acid methyl esters, the o-ethoxybenzoic acid ethyl ester, the o-ethoxybenzoic acid n-propyl, the o-ethoxybenzoic acid isopropyl ester, the positive butyl ester of o-ethoxybenzoic acid, o-methoxybenzoic acid isobutyl ester etc.
One of adduct of magnesium halides of the present invention more preferably embodiment is described MgX
2-mROH-nE-pH
2O, X are that chlorine, R are C
1-C
4Alkyl, m be 1.5-3.5, n is 0.02-0.3; R in the general formula (II)
1And R
2Identical or inequality, be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or isobutyl-.
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 magnesium halide, pure and mild o-alkoxyl benzoate compounds (or o-alkoxyl Benzoyl chloride) three components contact reacts under the condition of heating, final temperature of reaction will reach and can make magnesium halide, the fusing of pure and mild o-alkoxyl benzoate compounds form melt, be preferably 100 ℃～140 ℃, in the refrigerative inert media, further solidify to form solid particulate then.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 o-alkoxyl benzoate compounds (or o-alkoxyl Benzoyl chloride) 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 reactor,, under agitation mixture heating up is warmed up to 100-140 ℃, to the melt that forms adducts with magnesium halide, alcohol, o-alkoxyl benzoate compounds (or o-alkoxyl Benzoyl chloride) 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 o-alkoxyl benzoate compounds (or o-alkoxyl Benzoyl chloride) is respectively in every mole of magnesium: 1～5 and 0.005～1.
Minor amount of water in magnesium halide and the alcohol can participate in forming the reaction of adducts.
In the preparation of adduct of magnesium halides melt, order of addition(of ingredients) in no particular order.
2. the spherical adduct particulate forms
Above-mentioned adducts melt is put into the refrigerative inert media after high shear forces, form the spherical adduct particle.High shear forces can adopt conventional method, as high-speed mixing method (as Chinese patent CN1330086), spray method (as US6020279) and high-gravity rotating bed (preparation method described in CN1580136A) and mulser (the disclosed preparation method of 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-40 ℃～0 ℃.
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, common needs according to practical application can randomly add the known internal electron donor compound of some industry.
It is worthy of note, spherical adduct by magnesium halide, pure and mild o-alkoxyl benzoate compounds ternary component of the present invention, catalyzer as preparing carriers, be used for olefinic polymerization particularly during propylene polymerization, under high hydrogen concentration, the polymkeric substance of the high fusion index that obtains and have higher degree of isotacticity, the fine powder (fragmentation) of polymkeric substance obviously reduces simultaneously.
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.
Embodiment 1
Ball type carrier preparation: in the autoclave of 0.5L, add white oil 150ml, magnesium chloride 30g, ethanol 50ml and 3ml o-methoxy benzoyl chloride, under agitation be warmed up to 125 ℃, stirred 2.5 hours down at 125 ℃, mixture put into 120 ℃ silicone oil, stirred 45 minutes, and put in advance the 2L hexane that is cooled to-30 ℃ then, form the spherical solid particle, elimination liquid, with hexane wash solid five times, vacuum-drying, obtain the spherical magnesium chloride adducts carriers of 50 grams.(D50) be 80 microns, size distribution value (D50/ (D90-D10)) is 1.2.
Embodiment 2
A. the preparation of spherical catalyst
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 embodiment 1, be warming up to 110 ℃, in temperature-rise period, add diisobutyl phthalate 1.5ml, 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, CHMMS (cyclohexyl dimethoxy silane) 0.05mmol, the above-mentioned spherical catalyst 10mg that obtains, hydrogen 1.5L (standard volume) is warmed up to 70 ℃, polymerization 1 hour.Test result such as table 1,2.
Embodiment 3
In propylene polymerization, add the hydrogen 5.0L, with embodiment 2.
Embodiment 4
In propylene polymerization, add the hydrogen 8.0L, with embodiment 2.
Embodiment 5
Except that Preparation of catalysts replaces the diisobutyl phthalate, with embodiment 2 with n-butyl phthalate.
Embodiment 6
Except that propylene polymerization hydrogen 5.0L, with embodiment 5.
Embodiment 7
Except that propylene polymerization hydrogen 8.0L, with embodiment 5
Comparative Examples 1
Except that not adding the o-methoxy benzoyl chloride, with embodiment 1.Obtain the spherical magnesium chloride adducts carrier of 45 grams.Particle diameter (D50): 61.8 microns, size distribution value (D50/ (D90-D10)): 1.2.
Comparative Examples 2
Except that Preparation of Catalyst with the spherical magnesium chloride adducts of Comparative Examples 1 with embodiment 2.
Comparative Examples 3
Except that propylene polymerization hydrogen 5.0L, with Comparative Examples 2.
Comparative Examples 4
Except that propylene polymerization hydrogen 8.0L, with Comparative Examples 2.
Comparative Examples 5
The ball type carrier preparation: remove with 2, the 2-Propanal dimethyl acetal replaces o-methoxy benzoyl chloride outer with embodiment 1.
Preparation of Catalyst: except that with the magnesium chloride alcohol adduct carrier of Comparative Examples 5 with embodiment 2.
Polymerization: except that difference hydrogenation 1.5L, 5.0L and 8.0L, with embodiment 2.
The performance of table 1 catalyzer
The size distribution of table 2 polymkeric substance
| Embodiment | The above wt% of 10 orders | 10-20 order wt% | 20-40 order wt% | 40-60 order wt% | The following wt% of 60 orders |
| Embodiment 2 | 40.5 | 46.2 | 10.4 | 1.3 | 1.5 |
| Embodiment 3 | 49.8 | 42.9 | 5.6 | 0.8 | 1.0 |
| Comparative Examples 2 | 10.0 | 37.3 | 42.1 | 4.5 | 6.6 |
By the data of table 1 more as can be seen, be used for propylene polymerization by the prepared catalyzer of magnesium chloride adducts of the present invention, the polymkeric substance that the polymkeric substance that obtains has higher degree of isotacticity, particularly high fusion index still has higher degree of isotacticity, and the decline of degree of isotacticity is not obvious.
The data of table 2 more as can be seen, when being used for propylene polymerization by the prepared catalyzer of magnesium chloride adducts of the present invention, the fine powder content of polymkeric substance is lower, has reduced broken phenomenon significantly.
Claims (9)
1, a kind of adduct of magnesium halides is shown in general formula (I).
MgX
2-mROH-nE-pH
2O
(I)
In the general formula (I), X is a chlorine or bromine, and R is C
1-C
12Alkyl, C
3-C
10Cycloalkyl or C
6-C
10Aryl, E are the o-alkoxyl benzoate compounds shown in the general formula (II):
In the general formula (II), R
1And R
2Identical or different, be C
1-C
12The alkyl of straight or branched, C
3-C
10Cycloalkyl or C
6-C
10Aryl, C
7-C
10Alkaryl or aralkyl; R
1, R
2With R can be identical or different;
In the general formula (I), m is 1.0-5.0; N is 0.005-1.0; P is 0-0.8.
2, adduct of magnesium halides according to claim 1, in the wherein said general formula (I), R is C
1-C
4Alkyl.
3, adduct of magnesium halides according to claim 1, in the wherein said general formula (II), R
1And R
2Identical or inequality, be selected from C
1-C
6The alkyl of straight or branched.
4, adduct of magnesium halides according to claim 1, in the wherein said general formula (II), R
1And R
2Identical or inequality, be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or isobutyl-.
5, adduct of magnesium halides according to claim 1, in the wherein said general formula (I), m is 1.5-3.5, n is 0.02-0.3.
6, adduct of magnesium halides according to claim 1, in the wherein said general formula (I), R is C
1-C
4Alkyl, X is a chlorine, m is 1.5-3.5, n is 0.02-0.3; R in the general formula (II)
1And R
2Identical or inequality, be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or isobutyl-.
According to the described adduct of magnesium halides of one of claim 1-6, it is characterized in that 7, described adduct of magnesium halides is spherical.
8, the preparation method of the described adduct of magnesium halides of one of claim 1-6, it comprises following steps:
(1) preparation of adduct of magnesium halides melt
In reactor, with magnesium halide, alcohol, o-alkoxyl benzoate compounds and randomly inert media mixing, under agitation mixture heating up is warmed up to 100-140 ℃, 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 o-alkoxyl benzoate compounds is respectively in every mole of magnesium: 1～5 and 0.005～1;
(2) the adduct of magnesium halides particulate forms
Above-mentioned adduct of magnesium halides melt after high shear forces, is put into heat-eliminating medium and formed spherical adduct of magnesium halides particle, and the temperature of heat-eliminating medium is controlled at-40 ℃～0 ℃.
9, the application of the described adduct of magnesium halides of one of claim 1-6 in the preparation olefin polymerization catalysis.
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| IT1136627B (en) * | 1981-05-21 | 1986-09-03 | Euteco Impianti Spa | SUPPORTED CATALYST FOR THE POLYMERIZATION OF ETHYLENE |
| CN1169845C (en) * | 2002-02-07 | 2004-10-06 | 中国石油化工股份有限公司 | Solid catalyst component for olefine polymerization, catalyst with the component and its application |
| CN100491410C (en) * | 2006-04-06 | 2009-05-27 | 中国石油化工股份有限公司 | Adduct of magnesium halides, preparation method, and application |
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