CN101684165B - Magnesium halide adduct and preparation method and application thereof - Google Patents
Magnesium halide adduct and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a magnesium halide adduct, which is shown in the general formula (I) MgX2-mROH-kE-pF-qH2O. In the formula, X is chloride or bromine, and R is C1-C12 alkyl, C3-C10 naphthenic or C6-C10 aryl; E is a C, C-dioxyl hydrocarbon compound shown in the general formula (II); and F is a polyethenoxy ether compound shown in the general formula (III), wherein in the general formula (I), m is between 1 and 5, k is between 0 and 1.0, p is between 0.001 and 1.0, and q is between 0 and 0.8; and in the general formula (III), n is more than or equal to 1 and is less than or equal to 100.
Description
Technical field
The present invention relates to a kind of adduct of magnesium halides.More particularly, relate to the spherical adduct that a kind of magnesium halide, alcohol, electron donor compound and T 46155 ether compound four-tuple are divided, and the application of this adducts in the preparation olefin polymerization catalysis.
Background technology
Magnesium halide/alcohol adducts with and be known in the art as carrier being applied in olefin polymerization catalysis preparation.Obtain spherical catalyst after the reaction of this adducts and halogenated titanium and electron donor compound, be used for olefinic polymerization particularly during propylene polymerization, have very high polymerization activity and upright structure directional property, resulting polymkeric substance also has good particle form.
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 through 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 the preparation of this type magnesium chloride alcohol adduct is used for olefinic polymerization, in polymerization process, is easy to take place the broken phenomenon of catalyzer (polymkeric substance) particle, thereby causes fine polymer powder more.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, formed " magnesium dichloride-alcohol-phthalic ester " ball type carrier, then this carrier and titanium tetrachloride reaction are formed catalyzer.
In the disclosed technology of Chinese patent CN101050245A, C, C-two hydrocarbon oxy compounds are introduced in the carrier, and the spherical catalyst of preparation has better hydrogen regulation sensitivity, and fine powder content has certain minimizing in the polymkeric substance.
The inventor finds under study for action; After in the preparation of adduct of magnesium halides ball type carrier, introducing electron donor compound (the 3rd component); Sometimes the particle form of carrier particle is also unsatisfactory; As phenomenons such as abnormity material such as oblate spheroid, bar shaped particle, carrier particle size instability and carrier particle are clamminess appear easily, be unfavorable for the industrial production of carrier and the industrial application of catalyzer thereof.
Therefore; Being starved of provides a kind of new adduct of magnesium halides ball type carrier; This carrier size of particles in the preparation process is controlled, and the carrier particle particle form is good, and it is being used for olefinic polymerization particularly during propylene polymerization; Have higher hydrogen response, also have the particle form of better polymkeric substance simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of adduct of magnesium halides; This adduct of magnesium halides size of particles in the preparation process is controlled; The carrier particle particle form is good, particularly has the higher hydrogen response and the better particle form of polymkeric substance during propylene polymerization being used for olefinic polymerization.
A kind of adduct of magnesium halides, shown in the general formula (I):
MgX
2-mROH-kE-pF-qH
2O
(I)
In the general formula (I), X is a chlorine or bromine, and perhaps one of them X is replaced by following groups: C
1～C
14Alkyl, C
6～C
14Aryl, C
1～C
14Alkoxyl group and C
6～C
14Aryloxy; R is C
1～C
12Alkyl, C
3～C
10Naphthenic base or C
6～C
10Aryl; E is the C shown in the general formula (II), C-two-oxyl hydrocarbon compounds; F is the T 46155 ether compound shown in the general formula (III):
In the general formula (II), R
1, R
2, R
3Identical or different with R4, be hydrogen or C
1-C
10Straight chain or C
3-C
10The alkyl of side chain, C
3-C
10Naphthenic base, C
6-C
10Aryl, C
7-C
10Alkaryl or aralkyl; R
1And R
2In the optional mutual bonding of two or more groups generate one or several condensed ring structure; The benzene ring hydrogen is randomly replaced by halogen atom in said aryl or alkaryl or the aryl;
In the general formula (III), R ' is C
1-C
30Straight chain alkoxyl group, C
3～C
100Branched alkoxy, C
3～C
100Cycloalkyloxy, C
6～C
100Aryloxy, C
7～C
100Aryloxy alkyl, C
7～C
100Aralkoxy; Wasserstoffatoms on the phenyl ring in wherein said aryl, alkaryl or the aralkyl can randomly be replaced by halogen atom;
In the general formula (I), m is 1～5, and k is 0～1.0, and p is 0.001～1.0, and q is 0～0.8;
In the general formula (III), 1≤n≤30.
In the general formula (I), said magnesium halide MgX
2In, X is a chlorine or bromine, is preferably chlorine.Described X also can be by C
1～C
14Alkyl or alkoxyl group, C
6～C
14Aryl or aryloxy replace.Concrete compound is like magnesium dichloride, dibrominated magnesium, chlorination phenoxy magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium etc., wherein preferred magnesium dichloride.Said halogenated magnesium compound can separately or mix and use.
Described alcohol roh, wherein R is C
1～C
12Alkyl, C
3～C
10Naphthenic base 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, terepthaloyl moietie, Ucar 35.
At the C of general formula (II), in the C-two-oxyl hydrocarbon compounds, 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, halogenophenyl, tolyl, benzyl halide base, indenyl, benzyl or styroyl.More preferably, R
1And R
2Group is selected from methyl, ethyl, propyl group, butyl, amyl group, base, sec.-propyl, isobutyl-and isopentyl.
It is one of following that C shown in the preferred formula (II), C-two-oxyl hydrocarbon compounds are selected from: 2, and 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.
In the Soxylat A 25-7 of general formula (III), R ' is any one in the following groups: C
1～C
30Straight chain alkoxyl group, C
3～C
100Branched alkoxy, C
3～C
100Cycloalkyloxy, C
6～C
100Aryloxy, C
7～C
100Aryloxy alkyl, C
7～C
100Aralkoxy; Wasserstoffatoms on the phenyl ring in wherein said aryl, alkaryl or the aralkyl is randomly replaced by halogen atom; 1≤n≤30.
More preferably, R ' is selected from C
5-C
30Straight chain alkoxyl group, C
6～C
30Aryloxy, C
7～C
30Aryloxy alkyl or aralkoxy, 1≤n≤20.Particularly, can be selected from one of following: heptan oxygen base, octyloxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, dodecyloxy, n-Hexadecane oxygen base, octadecane oxygen base, align butyl phenoxy, align Octylphenoxy, to the iso-octyl phenoxy, align Nonylphenoxy; And 1≤n≤20.
It is one of following that T 46155 ether compound shown in the preferred formula (III) is selected from: heptan oxygen base Soxylat A 25-7, octyloxy Soxylat A 25-7, the ninth of the ten Heavenly Stems oxygen base Soxylat A 25-7, dodecyloxy Soxylat A 25-7, octadecane oxygen base Soxylat A 25-7, normal-butyl phenol polyethenoxy ether, n-octyl Soxylat A 25-7, iso-octyl Soxylat A 25-7, n-nonyl Soxylat A 25-7; 1≤n≤20.
Magnesium halide alcohol adduct of the present invention can adopt the known magnesium halide alcohol adduct preparation method of the industry to prepare, and for example can extrude or method such as high-speed stirring through spraying drying, spray cooling, high pressure.Usually; Can be earlier with magnesium halide, alcohol, electron donor compound and T 46155 ether compound four components contact reacts under the condition of heating; Final temperature of reaction will reach the adducts fusing that can make magnesium halide, alcohol, electron donor compound and T 46155 ether compound and form melt; Be preferably 80 ℃～140 ℃, chilling further solidify to form solid particulate in inert media then.Said inert media generally adopts the lower inert hydrocarbon solvent of boiling point, like pentane, hexane, heptane, gasoline or petrol ether etc.When the contact reacts of magnesium halide, alcohol, electron donor compound and T 46155 ether compound four components, also can randomly add inert liquid medium.Described inert media generally adopts some liquid aliphatic family hydro carbons inert solvents, like kerosene, Yellow Protopet 2A, vash oil, white oil etc., when needing, also can randomly add some silicoorganic compound, like methyl-silicone oil etc.Above-mentioned all inert medias generally need pass through the strict water treatment that removes before use.
A kind of preparation method of adduct of magnesium halides of the present invention, it may further comprise the steps:
(1) preparation of adduct of magnesium halides melt
In airtight container, with magnesium halide MgX
2, alcohol roh, electron donor compd E and Soxylat A 25-7 compound F 17-hydroxy-corticosterone heat to 80 ℃～140 ℃ with optional inert media, forms the adduct of magnesium halides melt, carries out high speed shear then; The add-on of magnesium halide is 0.1mol～1.2mol/L inert media, and the add-on of alcohol, electron donor compound and T 46155 ether compound is respectively 1～5 mole, 0.005～1.0 mole and 0.001～1.0 mole in every mole of magnesium;
(2) spherical adduct of magnesium halides particulate forms
With above-mentioned adduct of magnesium halides melt after high speed shear,, form spherical adduct of magnesium halides particle through the moulding of low temperature inert media chilling.
In the preparation of adduct of magnesium halides melt; It is to utilize its chemical reaction with magnesium halide, alcohol, electron donor to adjust the molecular polarity that reacts the gained adducts that the T 46155 ether compound is introduced; And then the IT of change adducts solution and dispersion medium, improve the particle morphology and the distribution thereof of adducts solid particulate.T 46155 ether compound according to the invention is a kind of of emulsion system tensio-active agent commonly used in fact, and is quite ripe in the research that the absorption of liquid/liquid interface improves the emulsion system IT through them.When T 46155 ether compound according to the invention is that the n value in the compound is 1～30 shown in the general formula (III); Particularly 1～20 o'clock; All can play the adjusting of good IT to liquid/liquid two mutually; Because will reaching the adducts fusing that can make magnesium halide, alcohol, electron donor compound and T 46155 ether compound, the final temperature of reaction of the present invention forms melt; Be preferably 100 ℃～140 ℃, so the present invention does not receive the influence of the compound proterties variation that the increase because of n value in the general formula (III) causes (along with the increase of n value, the T 46155 ether compound is by liquid state → paste → solid-state) basically.
In the preparation of adduct of magnesium halides melt; It is reinforced simultaneously with magnesium halide, alcohol, electron donor compound and inert media that the T 46155 ether compound can be chosen wantonly; At high temperature carry out high-temperature fusion, perhaps after magnesium halide, alcohol, electron donor compound and inert media high-temperature fusion, join again in this melt.
Inert media adopts some silicoorganic compound; Like methyl-silicone oil, ethyl silicon oil, methylethyl silicone oil, phenyl silicone oil, methyl phenyl silicone oil etc.; Also can randomly add some liquid aliphatic family hydro carbons inert solvents, like kerosene, Yellow Protopet 2A, vash oil, white oil etc.Preferable methyl silicone oil can be without the water treatment that removes of strictness before using.
Minor amount of water in magnesium halide and the alcohol can participate in forming the reaction of adducts.
High shear forces can adopt conventional method; Like the disclosed high-speed mixing method of Chinese patent CN1330086; Like the disclosed spray method of US6020279, and disclosed high-gravity rotating bed, the disclosed preparation method who utilizes mulser of CN1463990 etc. that utilizes of CN1580136.
Heat-eliminating medium can adopt the lower inert hydrocarbon solvent of boiling point, like pentane, hexane, heptane, gasoline or petrol ether etc.With before material contacts, the temperature of heat-eliminating medium is controlled at-40 ℃～-20 ℃.
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.
Above-mentioned magnesium halide alcohol adduct is applied to prepare olefin polymerization catalysis.
The synthetic of catalyzer can be adopted known compound method, and like said adduct of magnesium halides particle is direct and halogenated titanium reaction, the needs according to practical application can randomly add the known internal electron donor compound of some industry usually.
Description of drawings
Fig. 1 is the optical microscope photograph of the carrier of embodiment 1.
Fig. 2 is the optical microscope photograph of the carrier of embodiment 2.
Fig. 3 is the optical microscope photograph of the carrier of Comparative Examples 1.
Fig. 4 is the optical microscope photograph of the carrier of Comparative Examples 2.
Embodiment
Further describe the present invention below in conjunction with embodiment, be not used for limiting scope of the present 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); Promptly get 2g exsiccant polymer samples, place extractor with boiling heptane extracting 6 hours, afterwards; Residuum is dried to constant weight, and resulting polymers weight (g) is degree of isotacticity with 2 ratio.
3, size distribution test: adduct of magnesium halides particulate median size and size-grade distribution are measured with Masters Sizer2000 particle size analyzer (being manufactured by MalvernInstruments Ltd).
4, the pattern of sample is observed through Nikon Eclipse E200 type opticmicroscope-JVC color video camera.
Embodiment 1
The preparation of A, carrier
In the reaction kettle of 500mL, add 150ml methyl-silicone oil, 30g magnesium chloride, 50ml ethanol and 9ml Propanal dimethyl acetal successively, under agitation be warming up to 125 ℃.After the isothermal reaction 2 hours, mixture is pressed in octyl phenol polyoxy ethene (n=1010) ether/methyl-silicone oil (1.5ml/350ml) that is preheated to 115 ℃, high-speed stirring was disperseed 30 minutes.Nitrogen is pressed in advance in the 2L hexane that is chilled to-30 ℃ then, elimination liquid, with hexane wash solids 5 times, vacuum-drying, spherical magnesium chloride adducts.Median size (D50) is 45.2 μ m, and ((D90-D10)/D50) is 0.96 to size distribution value SPAN.
The preparation of B, spherical catalyst
In the glass reaction bottle of 300mL, add 90ml titanium tetrachloride, 10ml hexane successively, be cooled to-20 ℃, add above-mentioned ball type carrier 8g, be warming up to 110 ℃.In temperature-rise period, add diisobutyl phthalate 1.5ml, elimination liquid washs secondary with titanium tetrachloride, with hexane wash three times, and must spherical catalyst after the vacuum-drying.
C, propylene polymerization
Liquid phase bulk propylene polymerization is in the stainless steel autoclave of 5L, to carry out.In nitrogen protection downhill reaction still, add 2.5L propylene, 1mmol triethyl aluminium solution, 0.05mmol methylcyclohexyl dimethoxy silane (CHMMS) solution, the above-mentioned catalyzer of 10mg and 5L hydrogen (standard volume) successively; Be warming up to 70 ℃; React after 1 hour cooling, release; Discharging is with weighing after the gained alfon drying.
Embodiment 2
Remove the mixed solution China and foreign countries that octyl phenol polyoxy ethene (n=10) ether joined magnesium chloride, ethanol, Propanal dimethyl acetal and methyl-silicone oil, all the other are with embodiment 1.Gained ball type carrier median size D50 is 44.2 μ m, and size distribution value SPAN is 1.0.
Comparative Examples 1
Except that not adding octyl phenol polyoxy ethene (n=1010) ether, all the other are with embodiment 1.Gained ball type carrier median size D50 is 40.0 μ m, and size distribution value SPAN is 0.78.
Comparative Examples 2
Except that not adding octyl phenol polyoxy ethene (n=1010) ether, reach used inert dispersion medium and change into outside white oil/silicone oil (volume ratio is 1:2) mixture, all the other are with embodiment 1.Gained ball type carrier median size D50 is 50.3 μ m, and size distribution value SPAN is 1.2.
Fig. 1, Fig. 2 are the electromicroscopic photograph of embodiment 1 and embodiment 2 carriers, and Fig. 3, Fig. 4 are the electromicroscopic photograph of Comparative Examples 1 and Comparative Examples 2 carriers.Can be found out that by accompanying drawing the carrier granule form of the Comparative Examples among Fig. 3, Fig. 4 is bad, size of particles is uneven, also has more abnormity material.And from Fig. 1 and Fig. 2, can see adduct of magnesium halides carrier granule form of the present invention be improved significantly, and the carrier particle diameter is less, the carrier particle size is very even.
Polymerization result when table 1 has been listed catalyzer by embodiment 1,2 and Comparative Examples 1,2 gained preparing carriers and is used for propylene polymerization.Data from table relatively can find out, when being used for propylene polymerization by the prepared catalyzer of magnesium chloride adducts according to the invention, when keeping than high polymerization activity and higher stereotaxis ability, its hydrogen response also is significantly improved.
The performance of table 1 catalyzer
| Embodiment | Polymerization activity KgPP/gCat | Polymkeric substance I.I% | Polymkeric substance MIg/ml |
| Embodiment 1 | 40.1 | 96.4 | 30.4 |
| Embodiment 2 | 34.6 | 97.4 | 27.8 |
| Comparative Examples 1 | 45.1 | 96.6 | 24.8 |
| Comparative Examples 2 | 44.4 | 97.0 | 26 |
Claims (10)
1. adduct of magnesium halides, shown in general formula (I):
MgX
2-mROH-kE-pF-qH
2O
(I)
In the general formula (I), X is a chlorine or bromine, and perhaps one of them X is replaced by one of following groups: C
1～C
14Alkyl, C
6～C
14Aryl, C
1～C
14Alkoxyl group and C
6～C
14Aryloxy; R is C
1～C
12Alkyl, C
3～C
10Naphthenic base or C
6～C
10Aryl; E is the C shown in the general formula (II), C-two-oxyl hydrocarbon compounds; F is the T 46155 ether compound shown in the general formula (III):
In the general formula (II), R
1, R
2, R
3And R
4Identical or different, be hydrogen or C
1-C
10Straight chain or C
3-C
10The alkyl of side chain, C
3-C
10Naphthenic base, C
6-C
10Aryl, C
7-C
10Alkaryl or aralkyl, the benzene ring hydrogen is randomly replaced by halogen atom in said aryl or alkaryl or the aryl; R
1And R
2In the optional mutual bonding of two or more groups generate one or several condensed ring structure;
In the general formula (III), R ' is C
1-C
30Straight chain alkoxyl group, C
3～C
100Branched alkoxy, C
3～C
100Cycloalkyloxy, C
6～C
100Aryloxy, C
7～C
100Aryloxy alkyl, C
7～C
100Aralkoxy, the Wasserstoffatoms on the phenyl ring in wherein said aryl, alkaryl or the aralkyl can randomly be replaced by halogen atom;
In the general formula (I), m is 1～5, and k is 0.5～1.0, and p is 0.001～1.0, and q is 0～0.8;
In the general formula (III), 1≤n≤30.
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 (I), MgX
2Be magnesium dichloride, dibrominated magnesium, chlorination phenoxy magnesium, chlorination isopropoxy magnesium or chlorination butoxy magnesium.
4. adduct of magnesium halides according to claim 1, in the wherein said general formula (I), m is 1.5～3.5; K is 0.5～1.0; P is 0.01～0.4; Q is 0～0.8.
5. adduct of magnesium halides according to claim 1, in the wherein said general formula (II), R
1, R
2, R
3, R
4Be selected from methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, amyl group, cyclopentyl, cyclohexyl, phenyl, halogenophenyl, tolyl, benzyl halide base, indenyl, benzyl or styroyl; R
1, R
2, R
3, R
4Identical or different.
6. adduct of magnesium halides according to claim 5, in the wherein said general formula (II), R
1And R
2Be selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl, sec.-propyl, isobutyl-or isopentyl; R
1And R
2Identical or different.
7. adduct of magnesium halides according to claim 1, in the wherein said general formula (III), R ' is selected from and is C
5-C
30Straight chain alkoxyl group, C
6～C
30Aryloxy, C
7～C
30Aryloxy alkyl or aralkoxy, 1≤n≤20.
8. the preparation method of the described adduct of magnesium halides of claim 1 may further comprise the steps:
(1) preparation of adduct of magnesium halides melt
In airtight container, with magnesium halide MgX
2, alcohol roh, electron donor compd E and Soxylat A 25-7 compound F 17-hydroxy-corticosterone heat to 80 ℃～140 ℃ with optional inert media, forms the adduct of magnesium halides melt, carries out high speed shear then; The add-on of magnesium halide is 0.1 mole～1.2 mol inert medias, and the add-on of alcohol, electron donor compound and T 46155 ether compound is respectively 1～5 mole, 0.005～1.0 mole and 0.001～1.0 mole in every mole of magnesium;
(2) spherical adduct of magnesium halides particulate forms
With above-mentioned adduct of magnesium halides melt after high speed shear,, form spherical adduct of magnesium halides particle through the moulding of low temperature inert media chilling.
9. the preparation method of adduct of magnesium halides according to claim 8, wherein the inert media described in step (1) and the step (2) is a methyl-silicone oil.
10. the application of the described adduct of magnesium halides of claim 1 in the preparation olefin polymerization catalysis.
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| CN102796132B (en) * | 2011-05-27 | 2014-11-05 | 中国石油化工股份有限公司 | Spherical magnesium halide adduct and preparation method and application thereof |
| CN103788246B (en) * | 2012-10-29 | 2015-10-21 | 中国石油化工股份有限公司 | A kind of carrier for olefin polymerization catalyst and its preparation method and application |
| CN103788242B (en) * | 2012-10-29 | 2016-01-13 | 中国石油化工股份有限公司 | Catalyst solid component of olefin polymerization and preparation method thereof and olefin polymerization catalysis and application thereof |
| CN108219040B (en) * | 2018-01-09 | 2020-07-17 | 为信（深圳）材料科技有限公司 | Components, preparation method and application of spherical alkoxy magnesium particles |
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| CN101050245A (en) * | 2006-04-06 | 2007-10-10 | 中国石油化工股份有限公司 | Adduct of magnesium halides, preparation method, and application |
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