CN101050245A - Adduct of magnesium halides, preparation method, and application - Google Patents
Adduct of magnesium halides, preparation method, and application Download PDFInfo
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Abstract
This invention provides a kind of magnesium halide adducts, whose general chemical formula is MgX2-mROH-nE-pH2O (I), wherein, X is Cl or Br; R is C1-C12 alkyl, C3-C10 cycloalkyl or C6-C10 aryl; E is dialkoxy hydrocarbon compound as shown in formula (II); m is 1-5; n is 0.005-1.0; p is 0-0.8. In formula (II), R1, R2, R3 and R4 are the same or different, and are H or C1-C10 linear or branched alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C7-C10 alkylaryl or arylalkyl; two or more groups of R1 and R2 can bond into one or several fused rings; H is aryl or alkylaryl or H in benzene ring of arylalkyl can be substituted by halogen.
Description
Technical field
The present invention relates to a kind of adduct of magnesium halides and its production and application.More particularly, relate to a kind of magnesium halide, pure and mild C, the spherical adduct of C-two hydrocarbon oxy compound ternary components, 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.
In addition, the catalyzer of above-mentioned magnesium chloride alcohol adduct preparing carriers is when being used for the polyreaction of propylene, because hydrogen response is not ideal, can't satisfy the requirement that polypropylene industrial is produced.
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 have excellent comprehensive performances by its prepared olefin polymerization catalysis, particularly have better hydrogen regulation sensitivity, the particle form of resulting polymers is better.
Summary of the invention
The invention provides a kind of adduct of magnesium halides, it is for containing magnesium halide, pure and mild C, the spherical adduct of C-two-oxyl hydrocarbon compound ternary components.With the catalyzer of this adducts,, higher hydrogen response and better polymerization composition granule form have been shown being used for olefinic polymerization particularly during propylene polymerization as preparing carriers.
A kind of adduct of magnesium halides is shown in general formula (I).
MgX
2-mROH-nE-pH
2O
(I)
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 C shown in the general formula (II), C-two-oxyl hydrocarbon compounds:
R in the general formula (II)
1, R
2, R
3And R
4Can 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
1And R
2In two or more groups mutually bonding generate one or several condensed ring structure; The benzene ring hydrogen can randomly be replaced by halogen atom in described aryl or alkaryl or the aryl;
In the general formula (I), m is 1-5, preferred 1.5-3.5; N is 0.005-1.0, preferred 0.02-0.3; P is 0-0.8.
In the general formula (I), 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.
In two-oxyl hydrocarbon compounds of general formula (II), preferred R
1, R
2, R
3And R
4Group 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
1And R
2Group is selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl, sec.-propyl, isobutyl-and isopentyl.
Two-oxyl hydrocarbon compounds as:
2,2-Propanal dimethyl acetal, 2,2-dimethoxy-butane, 2,2-dimethoxy pentane, 3,3-dimethoxy pentane, 2,2-di ethyl propyl ether, 2,2-two phenoxypropanes 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.
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 C, C-two-oxyl hydrocarbon compounds three components are contact reacts under the condition of heating, final temperature of reaction will reach and can make magnesium halide, pure and mild C, the fusing of C-two-oxyl hydrocarbon compound adductss forms melt, be preferably 100 ℃～140 ℃, in 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.At magnesium halide, pure and mild C, during the contact reacts of C-two-oxyl hydrocarbon compounds 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 100-140 ℃, to forming the adduct of magnesium halides melt with magnesium halide, alcohol, two-oxyl hydrocarbon compounds and randomly inert media mixing.
The add-on of magnesium halide is 0.1～1.0mol/L liquid medium, pure and mild C, and the add-on of C-two-oxyl hydrocarbon compounds 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. 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-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 magnesium halide of the present invention, pure and mild C, the spherical adduct of C-two-oxyl hydrocarbon compound ternary components, catalyzer 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, catalyzer has higher hydrogen response.
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
In the autoclave of 1L, add white oil 110ml, 220ml silicone oil, 15 gram magnesium chloride, 28ml ethanol and 4ml Propanal dimethyl acetals, under agitation be warmed up to 125 ℃, stirred 3 hours down at 125 ℃, mixture is put in advance the 3L hexane that is cooled to-30 ℃, elimination liquid, with hexane wash solid three times, vacuum-drying obtains the 30.3 spherical magnesium chloride adductss that restrain, 50 microns of median sizes.
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 100 ℃, 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, CHMMS0.05mmol, spherical catalyst 10mg, hydrogen 5L (standard volume) is warmed up to 70 ℃, polymerization 1 hour.Test result such as table 1,2.
Embodiment 3
Except that the Propanal dimethyl acetal that replaces with 6ml, with embodiment 1.Get ball type carrier 31 grams, 61 microns of median sizes.
Embodiment 4
Except that the ball type carrier that replaces with embodiment 3, with embodiment 2.Test result such as table 1,2.
Comparative Examples 1
Except that not adding the Propanal dimethyl acetal, with embodiment 1.
Catalyzer system, propylene polymerization are with embodiment two.
The performance of table 1 catalyzer
| Embodiment | Polymerization activity kgPP/gcat | Polymkeric substance I.I % | Polymkeric substance MI g/ml |
| Embodiment 2 | 44.4 | 97.0 | 26 |
| Embodiment 4 | 54.0 | 96.9 | 27 |
| Comparative Examples 1 | 46.8 | 97.0 | 21 |
The size distribution of table 2 polymkeric substance
| Embodiment | The above wt% of 2mm | 2-0.9mm wt％ | 0.9-0.43mm wt％ | 0.43-0.3mm wt％ | 0.3mm following wt% |
| Embodiment 2 | 9.3 | 22.1 | 56.1 | 7.1 | 5.3 |
| Embodiment 4 | 18.3 | 67.5 | 10.9 | 1.6 | 1.7 |
| Comparative Examples 1 | 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, especially higher hydrogen response by the data of table 1;
More as can be seen, the fine powder that is used for the propylene polymerization resulting polymers by the prepared catalyzer of magnesium chloride adduction of the present invention is less, illustrates that the broken phenomenon of polymkeric substance obviously reduces by the data of table 2.
Claims (10)
1, a kind of adduct of magnesium halides is shown in general formula (I).
MgX
2-mROH-nE-pH
2O
(I)
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 two-oxyl hydrocarbon compounds shown in the general formula (II):
R in the general formula (II)
1, R
2, R
3And R
4Identical 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
1And R
2In two or more groups mutually bonding generate one or several condensed ring structure; The benzene ring hydrogen can randomly be replaced by halogen atom in described aryl or alkaryl or the aryl;
In the general formula (I), m is 1-5, and n is 0.005-1.0, and 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 C
1-C
10The 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, normal-butyl, amyl group, hexyl, sec.-propyl, isobutyl-or isopentyl.
5, adduct of magnesium halides according to claim 1, in the wherein said general formula (II), R
3And R
4Identical or inequality, be C
1-C
10The alkyl of straight or branched, C
6-C
10Aryl.
6, adduct of magnesium halides according to claim 1, in the wherein said general formula (II), R
3And R
4Identical or inequality, be methyl, ethyl, n-propyl, butyl, amyl group, hexyl, sec.-propyl or phenyl.
7, 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.
8, adduct of magnesium halides according to claim 1, in the wherein said general formula (I), R is C
1-C
4Alkyl, X is that chlorine, m are 1.5-3.5, n is 0.02-0.3.
9, 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, with magnesium halide, alcohol, two-oxyl hydrocarbon 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 two-oxyl hydrocarbon 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 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-40 ℃～0 ℃.
10, the application of the described adduct of magnesium halides of one of claim 1-8 in the preparation olefin polymerization catalysis.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100671779A CN100491410C (en) | 2006-04-06 | 2006-04-06 | Adduct of magnesium halides, preparation method, and application |
| EP07720696.9A EP2036928B1 (en) | 2006-04-06 | 2007-04-06 | Magnesium halide adduct, olefins polymerization catalyst component and catalyst made therefrom |
| KR1020087026783A KR101173267B1 (en) | 2006-04-06 | 2007-04-06 | Magnesium halide adduct, olefins polymerization catalyst component and catalyst made therefrom |
| SG2011072808A SG189559A1 (en) | 2006-04-06 | 2007-04-06 | Magnesium halide complexes, catalyst components and catalysts for olefin polymerization prepared therefrom |
| US12/294,980 US20100099833A1 (en) | 2006-04-06 | 2007-04-06 | Magnesium halide complexes, catalyst components and catalysts for olefin polymerization prepared therefrom |
| BRPI0709454A BRPI0709454B8 (en) | 2006-04-06 | 2007-04-06 | magnesium halide complex, process for preparing the olefin complex, catalyst for polymerization of an olefin and process for polymerizing olefins |
| MYPI20083967 MY151043A (en) | 2006-04-06 | 2007-04-06 | Magnesium halide adduct, olefins polymerization catalyst component and catalyst made therefrom |
| PCT/CN2007/001123 WO2007112700A1 (en) | 2006-04-06 | 2007-04-06 | Magnesium halide adduct, olefins polymerization catalyst component and catalyst made therefrom |
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