CN102796129B - A kind of Spherical magnesium halide adduct and its preparation method and application - Google Patents
A kind of Spherical magnesium halide adduct and its preparation method and application Download PDFInfo
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- CN102796129B CN102796129B CN201110142156.XA CN201110142156A CN102796129B CN 102796129 B CN102796129 B CN 102796129B CN 201110142156 A CN201110142156 A CN 201110142156A CN 102796129 B CN102796129 B CN 102796129B
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Abstract
The invention provides a kind of adduct of magnesium halides and its preparation method and application, the method comprises: the mixture obtained, by magnesium halide and the alcohol except methyl alcohol and the mixing of optional inert liquid medium, is under agitation heated to the melt forming adduct of magnesium halides by (1); (2) melt of described adduct of magnesium halides is added in heat-eliminating medium after shearing dissemination, form spherical solid particulate; (3) described spherical solid particulate and Propanal dimethyl acetal contact reacts in inert dispersion medium is made; (4) products therefrom and polyol ester compounds contact reacts in inert dispersion medium after step (3) contact.The particle form of adduct of magnesium halides according to the present invention is good, smooth surface, good fluidity, there will not be irregular particle, and use this adduct of magnesium halides as the catalyzer of catalyst support preparation, during for olefinic polymerization, there is good hydrogen response.
Description
Technical field
The present invention relates to a kind of adduct of magnesium halides, the preparation method of this adduct of magnesium halides, the adduct of magnesium halides prepared by described method, and described adduct of magnesium halides is as the application of support of the catalyst.
Background technology
Titanium compound and compound loaded metallocene (Ziegler-Natta) catalyzer of preparing in magnesium halide in active of electron donor are well known in the prior art.Usually, described magnesium halide in active adopts the adducts of magnesium halide and alcohol, obtains spherical catalyst after it can be used as carrier and halogenated titanium and electron donor compound to react.When this spherical catalyst being used for olefinic polymerization (particularly propylene polymerization), have higher polymerization activity and vertical structure directional property, the polymkeric substance obtained has good particle form.
The adducts of published magnesium halide and alcohol, generally includes magnesium chloride and alcohol binary composition.A small amount of water is also comprised in some published alcohol adduct.This type of alcohol adduct is extruded by spraying dry, spray cooling, high pressure or the method preparation such as high-speed stirring.As: the magnesium chloride alcohol adduct disclosed in US4421674, US4469648, WO8707620, WO9311166, US5100849, US6020279, US4399054, EP0395383, US6127304 and US6323152.When the catalyzer prepared of above-mentioned magnesium chloride alcohol adduct is for olefinic polymerization, is easy to the Fragmentation Phenomena that polymkeric substance occurs, thus causes fine polymer powder more.Its major cause may be that the catalyst active center formed on adducts carrier is uneven caused due in adducts and halogenated titanium and electron donor compound reaction process.
In order to overcome this shortcoming, people attempt again electron donor compound to introduce in advance in the carrier preparation of magnesium chloride alcohol adduct, such as: in CN1397568A and CN1563112A technology, by known for industry internal electron donor as phthalate compound is introduced in the synthesis of carrier, form " magnesium dichloride-alcohol-phthalic ester " mixture ball type carrier, then this carrier and titanium tetrachloride reaction are formed catalyzer.Disclosed ball type carrier is of a size of D50:70-200, and its catalyzer is used for propylene polymerization, and polymerization activity is lower, is 406gPP/gcat.Disclose a kind of adduct of magnesium halides at CN101050245A, its general formula is MgX
2-mROH-nE-pH2O, wherein, E is two-oxyl hydrocarbon compounds, and R is C1-C12 alkyl, C3-C10 cycloalkyl or C6-C10 aryl, and m is 1-5, n be 0.005-1.0, p is 0-0.8; The preparation method of this adduct of magnesium halides comprises: (1) in closed reactors, by magnesium halide, alcohol, two-oxyl hydrocarbon compounds and optionally inert media mixing, under agitation mixture is heated to 100-140 DEG C, to forming 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 alcohol and two-oxyl hydrocarbon compounds is respectively 1-5 and 0.005-1 in every mole of magnesium; (2) above-mentioned adduct of magnesium halides melt is put into heat-eliminating medium after high shear forces, form Spherical magnesium halide adduct particle, the temperature of heat-eliminating medium controls at-40 DEG C-0 DEG C.But, a large amount of irregular particles is there is according to adduct of magnesium halides prepared by the method for this patent application, as needle-shaped particle, clavate particle, use this adduct of magnesium halides as the catalyzer of carrier for olefinic polymerization time, resulting polymers can be caused undoubtedly also to there is a large amount of irregular particles.
Summary of the invention
First object of the present invention is the above-mentioned defect in order to overcome existing adduct of magnesium halides, provides a kind of adduct of magnesium halides with more regular three-dimensional arrangement.
Second object of the present invention is to provide the preparation method of described adduct of magnesium halides.
3rd object of the present invention is to provide the adduct of magnesium halides prepared by described method.
4th object of the present invention is to provide the application of described adduct of magnesium halides as support of the catalyst.
The invention provides a kind of adduct of magnesium halides, this adduct of magnesium halides contain compound that general formula is MgXY, compound, methyl alcohol and DOE that general formula is ROH, and containing or not moisture, wherein, in formula M gXY, X is halogen, and Y is halogen, C
1-C
14alkyl, C
1-C
14alkoxyl group, C
6-C
14aryl or C
6-C
14aryloxy; In general formula R OH, R is C
2-C
12alkyl, C
3-C
10cycloalkyl or C
6-C
10aryl, DOE is the polyol ester shown in general formula (I):
In general formula (I), R
1and R
2identical or different, and be the C of halogen, substituted or unsubstituted straight or branched separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl or C
2-C
20alkylene; R
3-R
6and R
1-R
2kidentical or different, and be the C of hydrogen, halogen, substituted or unsubstituted straight or branched separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl, C
2-C
20alkylene, C
2-C
20ester group, containing heteroatomic C
1-C
20alkyl, containing heteroatomic C
3-C
20cycloalkyl, containing heteroatomic C
6-C
20aryl, containing heteroatomic C
7-C
20aralkyl, containing heteroatomic C
2-C
20alkylene or R
3-R
6and R
1-R
2kin two or more bondings form saturated or undersaturated ring structure, described heteroatoms is one or more in halogen, nitrogen, oxygen, sulphur, silicon and phosphorus, and k is the integer of 0-10.
Present invention also offers a kind of preparation method of adduct of magnesium halides, the method comprises the following steps: compound and the mixing of optional inert liquid medium of (1) to be the compound of MgXY and general formula by general formula be ROH, under agitation the mixture obtained is heated to the melt forming adduct of magnesium halides, wherein, in formula M gXY, X is halogen, and Y is halogen, C
1-C
14alkyl, C
1-C
14alkoxyl group, C
6-C
14aryl or C
6-C
14aryloxy; In general formula R OH, R is C
2-C
12alkyl, C
3-C
10cycloalkyl or C
6-C
10aryl; (2) melt of described adduct of magnesium halides is added in heat-eliminating medium after shearing dissemination, form spherical solid particulate; (3) described spherical solid particulate and Propanal dimethyl acetal contact reacts in inert dispersion medium is made; (4) by products therefrom and DOE contact reacts in inert dispersion medium after step (3) contact, DOE is the polyol ester shown in general formula (I):
In general formula (I), R
1and R
2identical or different, and be the C of halogen, substituted or unsubstituted straight or branched separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl or C
2-C
20alkylene; R
3-R
6and R
1-R
2kidentical or different, and be the C of hydrogen, halogen, substituted or unsubstituted straight or branched separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl, C
2-C
20alkylene, C
2-C
20ester group, containing heteroatomic C
1-C
20alkyl, containing heteroatomic C
3-C
20cycloalkyl, containing heteroatomic C
6-C
20aryl, containing heteroatomic C
7-C
20aralkyl, containing heteroatomic C
2-C
20alkylene or R
3-R
6and R
1-R
2kin two or more bondings form saturated or undersaturated ring structure, described heteroatoms is one or more in halogen, nitrogen, oxygen, sulphur, silicon and phosphorus, and k is the integer of 0-10.
Present invention also offers the adduct of magnesium halides prepared by aforesaid method.
Present invention also offers the application of described adduct of magnesium halides of the present invention as support of the catalyst.
The present inventor is surprised to find that in experimentation, in the process preparing adduct of magnesium halides, after the adducts adopting Propanal dimethyl acetal and polyol ester compounds process magnesium halide and alcohol, not only the particle form of gained adduct of magnesium halides is good, smooth surface, good fluidity, there will not be irregular particle, and use this adduct of magnesium halides as the catalyzer of catalyst support preparation, during for olefinic polymerization, there is good hydrogen response.
Accompanying drawing explanation
Fig. 1 represents the optical microscope photograph of the adduct of magnesium halides of preparation in embodiment 1;
Fig. 2 represents the optical microscope photograph of the adduct of magnesium halides of preparation in comparative example 1;
Fig. 3 represents that the adduct of magnesium halides adopting embodiment 1 is as the optical microscope photograph of the olefin polymerization catalysis of catalyst support preparation.
Embodiment
According to a first aspect of the invention, the invention provides a kind of adduct of magnesium halides, wherein, this adduct of magnesium halides contains compound that general formula is MgXY, general formula is ROH compound, methyl alcohol and DOE, and containing or not moisture, wherein, in formula M gXY, X is halogen, and Y can be halogen, C
1-C
14alkyl, C
1-C
14alkoxyl group, C
6-C
14aryl or C
6-C
14aryloxy; In general formula R OH, R can be C
2-C
12alkyl, C
3-C
10cycloalkyl or C
6-C
10aryl; DOE is the polyol ester shown in general formula (I):
Wherein, R
1and R
2can be identical or different, and can be the C of halogen, substituted or unsubstituted straight or branched separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl or C
2-C
20alkylene; In formula (I), the contents table of bracket [] is shown with k carbon atom key company successively, and each carbon atom also replaces base key even with 2, i.e. total k carbon atom and R in bracket
1, R
2, R
3... R
2kdeng 2k substituting group, R
3-R
6and R
1-R
2kcan be identical or different, and can be the C of hydrogen, halogen, substituted or unsubstituted straight or branched separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl, C
2-C
20alkylene, C
2-C
20ester group, containing heteroatomic C
1-C
20alkyl, containing heteroatomic C
3-C
20cycloalkyl, containing heteroatomic C
6-C
20aryl, containing heteroatomic C
7-C
20aralkyl, containing heteroatomic C
2-C
20alkylene or R
3-R
6and R
1-R
2kin two or more bondings form saturated or undersaturated ring structure, described heteroatoms can be one or more in halogen, nitrogen, oxygen, sulphur, silicon and phosphorus, k is the integer of 0-10, and as k=0, then in the polyol ester shown in general formula (I), substituting group is R
3, R
4carbon atom directly and substituting group be R
5, R
6carbon atom key connect.Preferred R
1and R
2identical or different, can be halogen, C separately
1-C
12alkyl, C
3-C
12cycloalkyl, C
6-C
12aryl, C
7-C
12aralkyl or C
2-C
12alkylene; R
3-R
6, R
1-R
2kidentical or different, can be hydrogen, halogen, C separately
1-C
12alkyl, C
3-C
12cycloalkyl, C
6-C
12aryl, C
7-C
12aralkyl, C
2-C
12alkylene or C
2-C
12ester group.More preferably R
1and R
2identical or different, can be C separately
1-C
6alkyl, C
3-C
6cycloalkyl, C
6-C
8aryl or C
7-C
8aralkyl, be such as selected from the one in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, 3,5-dimethylphenyl, ethylbenzene, benzyl, methyl-benzyl or styroyl; R
3-R
6identical or different, can be hydrogen, C separately
1-C
6alkyl or C
3-C
6cycloalkyl, be such as selected from the one in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; R
1-R
2kidentical or different, can be hydrogen or C separately
1-C
4alkyl, be such as selected from the one in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or the tertiary butyl.
In the preferred case, described DOE is the binary alcohol esters shown in general formula (II):
Wherein, R
1and R
2identical with the definition in general formula (I); R
3'-R
6', R
7and R
8identical or different, and can be the C of hydrogen, halogen, straight or branched separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl, C
2-C
20alkylene, containing heteroatomic C
1-C
20alkyl, containing heteroatomic C
3-C
20cycloalkyl, containing heteroatomic C
6-C
20aryl, containing heteroatomic C
7-C
20aralkyl, containing heteroatomic C
2-C
20alkylene or R
3'-R
6' and R
7-R
8in two or more bondings form saturated or undersaturated ring structure, described heteroatoms can be one or more in halogen, nitrogen, oxygen, sulphur, silicon and phosphorus; Preferred R
1and R
2identical or different, can be halogen, C separately
1-C
12alkyl, C
3-C
12cycloalkyl, C
6-C
12aryl, C
7-C
12aralkyl or C
2-C
12alkylene; R
3'-R
6', R
7-R
8identical or different, can be hydrogen, halogen, C separately
1-C
12alkyl, C
3-C
12cycloalkyl, C
6-C
12aryl, C
7-C
12aralkyl or C
2-C
12alkylene.More preferably R
1and R
2identical or different, can be C separately
1-C
6alkyl, C
3-C
6cycloalkyl, C
6-C
8aryl or C
7-C
8aralkyl, be such as selected from the one in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, 3,5-dimethylphenyl, ethylbenzene, benzyl, methyl-benzyl or styroyl; R
3'-R
6' identical or different, can be hydrogen, C separately
1-C
6alkyl or C
3-C
6cycloalkyl, be such as selected from the one in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; R
7-R
8identical or different, can be hydrogen or C separately
1-C
4alkyl, be such as selected from the one in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or the tertiary butyl.
In the present invention, described binary alcohol esters can be such as 1,3-PD dibenzoate, 2-methyl isophthalic acid, ammediol dibenzoate, 2-ethyl-1,3-PD dibenzoate, 2，2-dimethyl-1，3-propanediol dibenzoate, (R)-1-phenyl-1,3-PD dibenzoate, 1,3-phenylbenzene-1,3-PD dibenzoate, 1,3-phenylbenzene-1,3-PD two n Propanoic acid ester, 1,3-phenylbenzene-2-methyl isophthalic acid, ammediol dipropionate, 1,3-phenylbenzene-2-methyl isophthalic acid, ammediol diacetate esters, 1,3-phenylbenzene-2，2-dimethyl-1，3-propanediol dibenzoate, 1,3-phenylbenzene-2，2-dimethyl-1，3-propanediol dipropionate, 1,3-di-t-butyl-2-ethyl-1,3-PD dibenzoate, 1,3-phenylbenzene-1,3-PD diacetate esters, 1,3-di-isopropyl-1,3-propyl alcohol two (4-butylbenzoic acid) ester, 1-phenyl-2-amino-1,3-propanediol dibenzoate, 1-phenyl-2-methyl isophthalic acid, 3-butyleneglycol dibenzoate, 2,4-glycol dibenzoate, 3-butyl-2,4-glycol dibenzoate, 3,3-dimethyl-2,4-glycol 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, 2-methyl isophthalic acid, 3-pentanediol two (Chlorodracylic acid) ester, 2-methyl isophthalic acid, 3-pentanediol two (p-methylbenzoic acid) ester, 2-butyl-1,3-pentanediol two (p-methylbenzoic acid) ester, 2-methyl isophthalic acid, 3-pentanediol two (p-tert-butyl benzoic acid) ester, 2-methyl isophthalic acid, 3-pentanediol pivalate, 2-methyl isophthalic acid, 3-pentanediol phenylformic acid laurate, 2,2-dimethyl-1,3-glycol dibenzoate, 2,2-dimethyl-1,3-pentanediol phenylformic acid laurate, 2-ethyl-1,3-glycol dibenzoate, 2-butyl-1,3-glycol dibenzoate, 2-allyl group-1,3-glycol dibenzoate, 2-methyl isophthalic acid, 3-glycol dibenzoate, 2-ethyl-1,3-glycol dibenzoate, 2-propyl group-1,3-glycol dibenzoate, 2-butyl-1,3-glycol 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 laurate, 1,3-pentanediol dipropionate, 2,2,4-trimethylammonium-1,3-pentanediol di-isopropyl manthanoate, 1-trifluoromethyl-3-methyl-2,4-glycol dibenzoate, 2,4-pentanediol, two pairs of fluoromethyl benzoic ethers, 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, 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, 4,4-dimethyl-3,5-heptanediol dibenzoate, 4,5-dimethyl-3,5-heptanediol dibenzoate, 4,6-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-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, two (benzoyloxy methyl) fluorenes of 9,9-, two ((meta-methoxy benzoyloxy) methyl) fluorenes of 9,9-, two ((m-chloro benzoyloxy) methyl) fluorenes of 9,9-, two ((to the chlorobenzene carboxyphenyl) methyl) fluorenes of 9,9-, two (Chinese cassia tree carboxymethyl group) fluorenes of 9,9-, 9-(benzoyloxy methyl)-9-(the third carboxymethyl group) fluorenes, two (the third carboxymethyl group) fluorenes of 9,9-, 9, two (propylene carboxymethyl group) fluorenes and 9 of 9-, one or more in two (neo-pentyl carboxymethyl group) fluorenes of 9-, cited binary alcohol esters can be commercially available, and also can adopt method well known in the art (method as described in reference CN1169845C) synthesis.
According to one embodiment of the present invention, the general formula of described adduct of magnesium halides can be expressed as MgXY-mROH-nCH
3oH-tDOE-qH
2o, wherein, in MgXY, X is halogen, and Y can be halogen, C
1-C
14alkyl, C
1-C
14alkoxyl group, C
6-C
14aryl or C
6-C
14aryloxy; In ROH, R can be C
2-C
12alkyl, C
3-C
10cycloalkyl or C
6-C
10aryl; M is 1-2.4, n be 0.1-1.0, t be 0.0001-0.1, q is 0-0.8; In the preferred case, in the general formula of above-mentioned adduct of magnesium halides, m is 1.5-2.2, n be 0.3-0.8, t be 0.0002-0.01, q is 0-0.5.
In the present invention, in formula M gXY, X and Y is halogen, or X is halogen, and Y can be C
1-C
6alkyl, C
1-C
6alkoxyl group, C
6-C
12aryl or C
6-C
12aryloxy.Described halogen is preferably chlorine or bromine.Described C
1-C
6alkyl can be such as methyl, ethyl, propyl group, sec.-propyl, butyl or isobutyl-, described C
1-C
6alkoxy as being methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy or isobutoxy, described C
6-C
12aryl can be such as phenyl, o-tolyl, a tolyl, p-methylphenyl, adjacent ethylbenzene, an ethylbenzene, to ethylbenzene or naphthyl, described C
6-C
12aryloxy can be such as phenoxy group or naphthyloxy.
Under further preferable case, general formula to be the compound of MgXY be in magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination butoxy magnesium one or more.
In the present invention, general formula is the alcohol that the compound of ROH refers to except methyl alcohol.In the preferred case, in general formula R OH, R is C
2-C
8alkyl, C
3-C
8cycloalkyl or C
6-C
10aryl.Described C
2-C
8alkyl can be such as ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl, hexyl, isohexyl, heptyl, different heptyl, octyl group or iso-octyl.Described C
3-C
8cycloalkyl can be such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.Described C
6-C
10aryl can be such as phenyl, o-tolyl, a tolyl, p-methylphenyl, adjacent ethylbenzene, an ethylbenzene, to ethylbenzene or naphthyl.
Under further preferable case, general formula to be the compound of ROH be in ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol and 2-Ethylhexyl Alcohol one or more.
In the preferred embodiment of the present invention, described adduct of magnesium halides is spheroidal particle, and the particle diameter of this spheroidal particle can be 10-100 μm, is preferably 20-80 μm.In this preferred implementation, the olefin polymerization catalysis formed as support of the catalyst by this adduct of magnesium halides has excellent crush resistance energy and hydrogen response.In the present invention, the average particulate diameter of spheroidal particle can adopt Mastersizer2000 laser particle analyzer to record.
According to a second aspect of the invention, present invention also offers a kind of preparation method of adduct of magnesium halides, the method comprises the following steps: compound and the mixing of optional inert liquid medium of (1) to be the compound of MgXY and general formula by general formula be ROH, under agitation the mixture obtained is heated to the melt forming adduct of magnesium halides, wherein, in formula M gXY, X is halogen, and Y can be halogen, C
1-C
14alkyl, C
1-C
14alkoxyl group, C
6-C
14aryl or C
6-C
14aryloxy; In general formula R OH, R can be C
2-C
12alkyl, C
3-C
10cycloalkyl or C
6-C
10aryl; (2) melt of described adduct of magnesium halides is added in heat-eliminating medium after shearing dissemination, form spherical solid particulate; (3) described spherical solid particulate and Propanal dimethyl acetal contact reacts in inert dispersion medium is made; (4) by products therefrom and DOE contact reacts in inert dispersion medium after step (3) contact, DOE is the polyol ester shown in general formula (I):
Wherein, R
1and R
2can be identical or different, and can be the C of halogen, substituted or unsubstituted straight or branched separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl or C
2-C
20alkylene; In formula (I), the contents table of bracket [] is shown with k carbon atom key company successively, and each carbon atom also replaces base key even with 2, i.e. total k carbon atom and R in bracket
1, R
2, R
3... R
2kdeng 2k substituting group, R
3-R
6and R
1-R
2kcan be identical or different, and can be the C of hydrogen, halogen, substituted or unsubstituted straight or branched separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl, C
2-C
20alkylene, C
2-C
20ester group, containing heteroatomic C
1-C
20alkyl, containing heteroatomic C
3-C
20cycloalkyl, containing heteroatomic C
6-C
20aryl, containing heteroatomic C
7-C
20aralkyl, containing heteroatomic C
2-C
20alkylene or R
3-R
6and R
1-R
2kin two or more bondings form saturated or undersaturated ring structure, described heteroatoms can be one or more in halogen, nitrogen, oxygen, sulphur, silicon and phosphorus, k is the integer of 0-10, and as k=0, then in the polyol ester shown in general formula (I), substituting group is R
3, R
4carbon atom directly and substituting group be R
5, R
6carbon atom key connect.In the preparation method of described adduct of magnesium halides, all with above described situation is identical with preferable case in the definition of MgXY, ROH of using and DOE etc., and therefore not to repeat here.
According to described method provided by the invention, in above-mentioned steps (1), the add-on of general formula to be the compound of MgXY and general formula the be compound of ROH suitably can be selected according to the proportioning of each component in the Spherical magnesium halide adduct gone for.Under preferable case, the mol ratio of general formula to be the compound of MgXY and general formula the be add-on of the compound of ROH is 1: 1-8, is preferably 1: 2-6.The compound of described general formula to be compound and the general formula of MgXY be ROH with describe above identical.
According to described method provided by the invention, in step (1), the object of described heating is the adduct melt in order to make magnesium halide, alcohol and inert liquid medium form magnesium halide and alcohol.The condition of described heating does not have concrete restriction, can determine according to the concrete halogenated magnesium compound used.Described heating condition can comprise usually: Heating temperature is more than 80 DEG C, and heat-up time is more than 1 hour.Under preferable case, described heating condition comprises: Heating temperature is 100-140 DEG C, and heat-up time is 1-5 hour.
According to described method provided by the invention, variously there is not chemically interactive liquid medium with adduct of magnesium halides in what the inert liquid medium used in step (1) can be commonly used for this area, such as: silicoorganic compound and/or aliphatic hydrocarbon based compound.Particularly, described inert liquid medium can be one or more in Skellysolve A, normal hexane, normal heptane, sherwood oil, gasoline, methyl-silicone oil, ethyl silicon oil, methylethyl silicone oil, phenyl silicone oil, methyl phenyl silicone oil, kerosene, paraffin oil, vaseline oil and white oil.Further in preferred situation, described inert liquid medium is white oil and silicone oil.There is no particular limitation for the consumption of described inert liquid medium, usually relative to 1 mole in the MgXY of magnesium (magnesium halide namely added in step (1)), the consumption of described inert liquid medium is 0.8-10L.
According to described method provided by the invention, in step (2), described shearing dissemination can adopt conventional method to implement, such as: high-speed mixing method disclosed in CN1330086C (that is, adduct of magnesium halides being stirred with the speed of 2000-5000 rev/min in inert liquid medium); CN1267508C is disclosed to carry out rotating (speed of rotation can be 1000-3000 rev/min) and disperses in hypergravity bed by adduct of magnesium halides and the mixture of inert liquid medium; CN1463990A is disclosed to be exported the mixture mulser of adduct of magnesium halides and silicone oil and white oil with the speed of 1500-8000 rev/min; US6020279 disclosed by spray method by the emulsifying mixture containing adduct of magnesium halides.
According to described method provided by the invention, in step (2), being added in heat-eliminating medium after shearing dissemination by the melt of described adduct of magnesium halides is in order to the melt supercooled of adduct of magnesium halides is formed spherical solid particulate.In the present invention, described heat-eliminating medium is preferably inert hydrocarbon solvent, is more preferably lower boiling inert hydrocarbon solvent, such as, can be one or more in pentane, hexane, heptane, gasoline or petrol ether.The temperature of described heat-eliminating medium can be-40 DEG C to 0 DEG C, is preferably-30 DEG C to-10 DEG C.
According to described method provided by the invention, after described chilling and before making solid particulate and Propanal dimethyl acetal contact reacts, described method preferably also comprises carries out washing 1-10 time with inert organic solvents to the solid particulate obtained after described chilling, then carries out drying.Described inert organic solvents can be such as one or more in pentane, hexane, heptane, gasoline or petrol ether.
According to described method provided by the invention, there is no particular limitation for the described catalytic condition in step (3), and under preferable case, described catalytic condition comprises: temperature of reaction is 40-65 DEG C, is more preferably 45-60 DEG C; Reaction times is 1-5 hour, is more preferably 2-4 hour; Relative to 1 mole in the MgXY of magnesium (magnesium halide namely added in step (1)), the add-on of the Propanal dimethyl acetal in step (3) is 0.1-1.5 mole, is more preferably 0.2-1.0 mole.
According to described method provided by the invention, in step (3), described inert dispersion medium can be such as at least one in pentane, hexane and heptane.
According to described method provided by the invention, in order to obtain the spheroidal particle of adduct of magnesium halides, described method can also comprise filters the product obtained after described contact reacts, with inert organic solvents washing 1-10 time.Described inert organic solvents can be identical or different with above-mentioned inert organic solvents.
Product after the spheroidal particle of described adduct of magnesium halides is contacted with Propanal dimethyl acetal, with polyol ester mix further contact when, the add-on of described polyol ester and general formula are the mol ratio of the add-on of the compound of MgXY can be 0.01-0.5, is preferably 0.02-0.2; Product after the spheroidal particle of described adduct of magnesium halides contacts with Propanal dimethyl acetal, can comprise with the condition of polyol ester mixing and contacting reaction: temperature is 40-65 DEG C, the time is 1-5 hour.Described polyol ester is the polyol ester shown in above-mentioned general formula (I), is preferably the binary alcohol esters shown in above-mentioned general formula (II).
According to described method provided by the invention, in step (4), described inert dispersion medium can be such as at least one in pentane, hexane and heptane.
According to described method provided by the invention, in order to obtain the spheroidal particle of adduct of magnesium halides, described method can also comprise the product after by described contact reacts and filter, and with inert organic solvents washing 1-10 time, then carries out drying.Described inert organic solvents can be identical or different with above-mentioned inert organic solvents.
According to a third aspect of the present invention, present invention also offers the adduct of magnesium halides prepared by aforesaid method.In the preferred case, described adduct of magnesium halides is spheroidal particle, and the particle diameter of this spheroidal particle can be 10-100 μm, is preferably 20-80 μm.
According to a fourth aspect of the present invention, present invention also offers the application of described adduct of magnesium halides of the present invention as support of the catalyst.Described adduct of magnesium halides of the present invention can directly as support of the catalyst for the production of catalyzer (such as, olefin polymerization catalysis).
The invention will be further described by the following examples.But should be understood that, these embodiments, only for instruction and explanation of the present invention, are not limited to the present invention.
Embodiment 1
The present embodiment is for illustration of described adduct of magnesium halides provided by the invention and its preparation method and application.
(1) preparation of magnesium chloride adducts
In the autoclave of 300L, add the ethanol (249.0mol) of the white oil of 90L, the silicone oil of 90L, the magnesium chloride (94.7mol) of 9.0kg and 14.5L, under agitation be warming up to 125 DEG C, and stir 2.5 hours at 125 DEG C, then, the mixing liquid obtained is cooled in the hexane of-30 DEG C by high-gravity rotating bed entering in advance, elimination liquid, and with after hexanes wash five times, vacuum-drying 2 hours at 40 DEG C, obtains the solid matter (i.e. the alcohol adduct of magnesium chloride) of 18kg.
In the reactor of 1.6L, add the hexane of 900ml, the solid matter of 90 grams of above-mentioned preparations is added wherein, again the Propanal dimethyl acetal solution (content of Propanal dimethyl acetal is 0.37mol) of the 45ml be dissolved in the hexane of 180ml is added wherein, then, be warming up to 60 DEG C, and stirring reaction 3h at such a temperature, carry out press filtration afterwards, with hexanes wash 2 times, add the hexane of 800ml, to be dissolved in the hexane of 100ml again 2 of 8ml, 4-glycol dibenzoate adds wherein, be warming up to 60 DEG C, and stirring reaction 2h at such a temperature, then press filtration is carried out, with hexanes wash 5 times, and spherical magnesium chloride adducts is obtained after dry 4 hours at 60 DEG C.
The Mg content in this spherical magnesium chloride adducts is detected according to complexometry, ethanol, the methyl alcohol and 2 in this spherical magnesium chloride adducts is detected respectively according to liquid chromatography analysis method, the content of 4-glycol dibenzoate, consequently, the mol ratio of the magnesium chloride in this magnesium chloride adducts, ethanol, methyl alcohol and 2,4-glycol dibenzoate is 1: 1.6: 0.6: 0.0005; Adopt Mastersizer2000 laser particle analyzer (being produced by MalvernInstrumentsLtd) to record, the average particulate diameter of this magnesium chloride adducts is 43 microns.
(2) preparation of olefin polymerization catalysis
In the glass reaction bottle of 2000ml, add the titanium tetrachloride of 500ml and be cooled to-20 DEG C, magnesium chloride adducts obtained in the embodiment 1 of 40 grams is added wherein, then 110 DEG C are warming up to, and in temperature-rise period, add 2 of 6.5ml, 2-sec.-propyl-2-the isopentyl-1 of 4-glycol dibenzoate and 6.5ml, 3-Propanal dimethyl acetal, elimination liquid maintain 30min at 110 DEG C after, add titanium tetrachloride afterwards again and wash 2 times, finally use hexanes wash 5 times, then vacuum-drying 2 hours at 40 DEG C, obtain olefin polymerization catalysis C1.Adopt NikonEclipseE200 type opticmicroscope-JVC color video camera to observe this catalyzer C1, its optical microscope photograph as shown in Figure 3.
(3) propylene polymerization
In the autoclave of a 5L, adopt stream of nitrogen gas to purge, in stream of nitrogen gas, then introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of the triethyl aluminum of 1ml, the hexane solution (concentration of CHMMS is 0.1mmol/ml) of the Cyclohexyl Methyl Dimethoxysilane (CHMMS) of 0.1ml, the anhydrous hexane of 10ml and the olefin polymerization catalysis C1 of 4mg.Close autoclave, add the hydrogen (standard volume) of 2.0L and the liquid propene of 2.3L, be warming up to 70 DEG C, and react 1 hour at such a temperature.
Embodiment 2
The present embodiment is for illustration of described adduct of magnesium halides provided by the invention and its preparation method and application.
Prepare magnesium chloride adducts according to the method for embodiment 1, prepare olefin polymerization catalysis and carry out propylene polymerization, difference is, in propylene polymerization process, the add-on of hydrogen is 6.5L.
Comparative example 1
(1) preparation of magnesium chloride adducts
In the autoclave of 300L, add white oil 90L, silicone oil 90L, magnesium chloride 9.0kg and ethanol 14.5L, under agitation be warmed up to 125 DEG C, and stir 2.5 hours at such a temperature, then, the mixing liquid obtained is cooled in the hexane of-30 DEG C by high-gravity rotating bed entering in advance, elimination liquid, and with hexanes wash five times, after drying, obtain the solid matter (i.e. the alcohol adduct of magnesium chloride) of 18kg.
(2) preparation of olefin polymerization catalysis
Prepare olefin polymerization catalysis according to the method for embodiment 1, obtain olefin polymerization catalysis DC1 unlike the magnesium chloride adducts adopting comparative example 1 step (1) to prepare.
(3) propylene polymerization
Propylene polymerization is carried out, unlike the use of catalyzer prepared by comparative example 1 step (2) according to the method for embodiment 1.
Comparative example 2
Prepare magnesium chloride adducts according to the method for comparative example 1, prepare olefin polymerization catalysis and carry out propylene polymerization, difference is, in propylene polymerization process, the add-on of hydrogen is 6.5L.
Embodiment 3
The present embodiment is for illustration of described adduct of magnesium halides provided by the invention and its preparation method and application.
(1) preparation of adduct of magnesium halides
Prepare magnesium chloride adducts according to the method for embodiment 1, difference is the add-on of Propanal dimethyl acetal is 10ml.
The Mg content in this spherical magnesium chloride adducts is detected according to complexometry, ethanol, the methyl alcohol and 2 in this spherical magnesium chloride adducts is detected respectively according to liquid phase chromatographic analysis method, the content of 4-glycol dibenzoate, consequently, the mol ratio of the magnesium chloride in this magnesium chloride adducts, ethanol, methyl alcohol and 2,4-glycol dibenzoate is 1: 2.2: 0.2: 0.0002; Adopt Mastersizer2000 laser particle analyzer (being produced by MalvernInstrumentsLtd) to record, the average particulate diameter of this magnesium chloride adducts is 43 microns.
(2) preparation of olefin polymerization catalysis
Prepare olefin polymerization catalysis according to the method for embodiment 1, obtain olefin polymerization catalysis C2 unlike the magnesium chloride adducts adopting embodiment 3 step (1) to prepare.
(3) propylene polymerization
Propylene polymerization is carried out, unlike the use of catalyzer prepared by embodiment 3 step (2) according to the method for embodiment 1.
Embodiment 4
The present embodiment is for illustration of described adduct of magnesium halides provided by the invention and its preparation method and application.
Prepare magnesium chloride adducts according to the method for embodiment 3, prepare olefin polymerization catalysis and carry out propylene polymerization, difference is, in propylene polymerization process, the add-on of hydrogen is 6.5L.
Test case 1
NikonEclipseE200 type opticmicroscope-JVC color video camera is adopted to observe the magnesium chloride adducts of preparation in embodiment 1 and comparative example 1, and the optical microscope photograph of the magnesium chloride adducts of embodiment 1 as shown in Figure 1, the optical microscope photograph of the magnesium chloride adducts of comparative example 1 as shown in Figure 2.
As can be seen from Fig. 1 and Fig. 2, the particle form of the magnesium chloride adducts of embodiment 1 is regular, and be all spherical substantially, particle size distribution is more concentrated, and there is no that irregular particle exists, and does not also have obvious broken particles; And have obvious broken particles in the magnesium chloride adduct particles of comparative example 1.
Test case 2
(1) melting index of polymkeric substance is detected according to the method for ASTMD1238-99:
(2) heptane extraction process is adopted to detect polymkeric substance degree of isotacticity, the method comprises: be placed in extractor by 2 grams of dry polymer samples, with the extracting of boiling heptane after 6 hours, residuum is dried to constant weight, and the polymer weight (g) of gained and the ratio of 2 are degree of isotacticity;
As shown in table 1 below according to the result that aforesaid method detects.
Table 1
As can be seen from the data of above-mentioned table 1, the adduct of magnesium halides adopting method of the present invention to obtain, as the catalyzer of catalyst support preparation, has good hydrogen response in propylene polymerization.Concrete, by by the melting index of the polymkeric substance obtained after adopting catalyzer C1 and C2 to carry out propylene polymerization respectively with adopt catalyzer DC1 to carry out propylene polymerization after the melting index of polymkeric substance that obtains compare and can find out, relative to catalyzer DC1, catalyzer C1 and C2 has good hydrogen response.
Test case 3
Sieved by polymkeric substance obtained in embodiment 1 and comparative example 1, its result is as shown in table 2 below:
Table 2
As can be seen from the data of upper table 2, in the process preparing propene polymer, adopt the fine powder content of the catalyzer be made up as support of the catalyst of described adduct of magnesium halides provided by the invention and obtained propene polymer less (particle size be below 80 orders be generally fine powder), visible, the catalyzer be made up of described adduct of magnesium halides provided by the invention is not easily broken, thus has good crush resistance.
Above embodiment is only for describing the preferred embodiment of the present invention; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (20)
1. an adduct of magnesium halides, is characterized in that, the general formula of this adduct of magnesium halides is MgXY-mROH-nCH
3oH-tDOE-qH
2o, wherein, m is 1-2.4, n be 0.1-1.0, t be 0.0001-0.1, q is 0-0.8, and in MgXY, X is halogen, and Y is halogen, C
1-C
14alkyl, C
1-C
14alkoxyl group, C
6-C
14aryl or C
6-C
14aryloxy; In ROH, R is C
2-C
12alkyl, C
3-C
10cycloalkyl or C
6-C
10aryl; DOE is the polyol ester shown in general formula (I):
R in DOE
1and R
2be halogen, C separately
1-C
12alkyl, C
3-C
12cycloalkyl, C
6-C
12aryl, C
7-C
12aralkyl or C
2-C
12alkylene; R
3-R
6, R
1-R
2kbe hydrogen, halogen, C separately
1-C
12alkyl, C
3-C
12cycloalkyl, C
6-C
12aryl, C
7-C
12aralkyl, C
2-C
12alkylene or C
2-C
12ester group; K is the integer of 0-10.
2. adduct of magnesium halides according to claim 1, wherein, m is 1.5-2.2, n be 0.3-0.8, t be 0.0002-0.01, q is 0-0.5.
3. adduct of magnesium halides according to claim 1 and 2, wherein, MgXY is one or more in magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination butoxy magnesium; ROH is one or more in ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol and 2-Ethylhexyl Alcohol.
4. adduct of magnesium halides according to claim 1, wherein, R in DOE shown in described general formula (I)
1and R
2be C separately
1-C
6alkyl, C
3-C
6cycloalkyl, C
6-C
8aryl or C
7-C
8aralkyl; R
3-R
6be hydrogen, C separately
1-C
6alkyl or C
3-C
6cycloalkyl; R
1-R
2kbe hydrogen or C separately
1-C
4alkyl.
5. adduct of magnesium halides according to claim 1, wherein, described DOE is the binary alcohol esters shown in general formula (II):
In general formula (II), R
1and R
2be halogen, C separately
1-C
12alkyl, C
3-C
12cycloalkyl, C
6-C
12aryl, C
7-C
12aralkyl, C
2-C
12alkylene; R
3'-R
6', R
7-R
8be hydrogen, halogen, C separately
1-C
12alkyl, C
3-C
12cycloalkyl, C
6-C
12aryl, C
7-C
12aralkyl or C
2-C
12alkylene.
6. adduct of magnesium halides according to claim 5, wherein, in general formula (II), R
1and R
2be C separately
1-C
6alkyl, C
3-C
6cycloalkyl, C
6-C
8aryl or C
7-C
8aralkyl; R
3'-R
6' be hydrogen, C separately
1-C
6alkyl or C
3-C
6cycloalkyl; R
7-R
8identical or different, be hydrogen or C separately
1-C
4alkyl.
7. adduct of magnesium halides according to claim 1, wherein, described adduct of magnesium halides is spheroidal particle, and the average particulate diameter of this spheroidal particle is 10-100 micron.
8. a preparation method for adduct of magnesium halides according to claim 1, the method comprises the following steps:
(1) compound and the mixing of optional inert liquid medium of to be the compound of MgXY and general formula by general formula be ROH, under agitation the mixture obtained is heated to the melt forming adduct of magnesium halides, wherein, in formula M gXY, X is halogen, and Y is halogen, C
1-C
14alkyl, C
1-C
14alkoxyl group, C
6-C
14aryl or C
6-C
14aryloxy; In general formula R OH, R is C
2-C
12alkyl, C
3-C
10cycloalkyl or C
6-C
10aryl;
(2) melt of described adduct of magnesium halides is added in heat-eliminating medium after shearing dissemination, form spherical solid particulate;
(3) described spherical solid particulate and Propanal dimethyl acetal contact reacts in inert dispersion medium is made;
(4) by products therefrom and DOE contact reacts in inert dispersion medium after step (3) contact, DOE is the polyol ester shown in general formula (I):
R in DOE
1and R
2be halogen, C separately
1-C
12alkyl, C
3-C
12cycloalkyl, C
6-C
12aryl, C
7-C
12aralkyl or C
2-C
12alkylene; R
3-R
6, R
1-R
2kbe hydrogen, halogen, C separately
1-C
12alkyl, C
3-C
12cycloalkyl, C
6-C
12aryl, C
7-C
12aralkyl, C
2-C
12alkylene or C
2-C
12ester group; K is the integer of 0-10.
9. method according to claim 8, wherein, in step (1), the temperature of described heating is 100-140 DEG C, and the time of described heating is 1-5 hour; The mol ratio of general formula to be the compound of MgXY and general formula the be add-on of the compound of ROH is 1:1-8; Relative to 1 mole in the MgXY of magnesium, the consumption of described inert liquid medium is 0.8-10L, and described inert liquid medium is silicoorganic compound and/or aliphatic hydrocarbon based compound.
10. method according to claim 8, wherein, the general formula in step (1) to be the compound of MgXY be in magnesium dichloride, dibrominated magnesium, phenoxy group magnesium chloride, isopropoxy magnesium chloride and butoxy magnesium chloride one or more; General formula to be the compound of ROH be in ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol and 2-Ethylhexyl Alcohol one or more.
11. methods according to claim 8, wherein, in step (2), described heat-eliminating medium is inert hydrocarbon solvent; The temperature of described heat-eliminating medium is-40 DEG C to 0 DEG C.
12. methods according to claim 11, wherein, described heat-eliminating medium is one or more in pentane, hexane, heptane, gasoline or petrol ether; The temperature of described heat-eliminating medium is-30 DEG C to-10 DEG C.
13. methods according to claim 8, wherein, the described catalytic condition in step (3) comprises: temperature of reaction is 40-65 DEG C, and the reaction times is 1-5 hour, relative to 1 mole in the MgXY of magnesium, the add-on of described Propanal dimethyl acetal is 0.1-1.5 mole.
14. methods according to claim 13, wherein, the add-on of described Propanal dimethyl acetal is 0.2-1.0 mole.
15. methods according to claim 8, wherein, R in DOE shown in the described general formula (I) in step (4)
1and R
2be C separately
1-C
6alkyl, C
3-C
6cycloalkyl, C
6-C
8aryl or C
7-C
8aralkyl; R
3-R
6be hydrogen, C separately
1-C
6alkyl or C
3-C
6cycloalkyl; R
1-R
2kbe hydrogen or C separately
1-C
4alkyl.
16. methods according to claim 8, wherein, the described DOE in step (4) is the binary alcohol esters shown in general formula (II):
In general formula (II), R
1and R
2be halogen, C separately
1-C
12alkyl, C
3-C
12cycloalkyl, C
6-C
12aryl, C
7-C
12aralkyl, C
2-C
12alkylene; R
3'-R
6', R
7-R
8be hydrogen, halogen, C separately
1-C
12alkyl, C
3-C
12cycloalkyl, C
6-C
12aryl, C
7-C
12aralkyl or C
2-C
12alkylene.
17. methods according to claim 16, wherein, in general formula (II), R
1and R
2be C separately
1-C
6alkyl, C
3-C
6cycloalkyl, C
6-C
8aryl or C
7-C
8aralkyl; R
3'-R
6' be hydrogen, C separately
1-C
6alkyl or C
3-C
6cycloalkyl; R
7-R
8identical or different, be hydrogen or C separately
1-C
4alkyl.
18. methods according to claim 8, wherein, the described catalytic condition in step (4) comprises: temperature of reaction is 40-65 DEG C, and the reaction times is 1-5 hour, relative to 1 mole in the MgXY of magnesium, the add-on of described DOE is 0.01-0.5 mole.
19. methods according to claim 18, wherein, the add-on of described DOE is 0.02-0.2 mole.
Adduct of magnesium halides in 20. claim 1-7 described in any one is as the application of support of the catalyst.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110142156.XA CN102796129B (en) | 2011-05-27 | 2011-05-27 | A kind of Spherical magnesium halide adduct and its preparation method and application |
| IT000877A ITMI20120877A1 (en) | 2011-05-27 | 2012-05-22 | MAGNESIUM HALOGENUR ADDOTTO, CATALYTIC COMPONENT / CATALYST INCLUDING MAGNESIUM HALOGENURED PARTICLE AND ITS PREPARATION. |
| BE2012/0343A BE1022065B1 (en) | 2011-05-27 | 2012-05-23 | MAGNESIUM HALIDE REGENERATION PRODUCT, CATALYTIC COMPONENT AND CATALYST COMPRISING SAME, AND THEIR PREPARATION |
| TW101118766A TWI473827B (en) | 2011-05-27 | 2012-05-25 | Magnesium halide adducts, catalyst components including them and catalysts, and the above-mentioned production methods and applications |
| BR102012012599-4A BR102012012599B1 (en) | 2011-05-27 | 2012-05-25 | MAGNESIUM HALOGENE ADUCT, CATALYST COMPONENT FOR OLEFIN POLYMERIZATION, PROCESS FOR PREPARATION OF CATALYST COMPONENT FOR OLEFIN POLYMERIZATION, PROCESS FOR PREPARATION OF A CATALYST FOR POLYMERIZATION OF OLEFINS, CATALYST FOR POLYMERIZATION OF OLEFINS AND PROCESS OLEFINS |
| FR1254853A FR2975607B1 (en) | 2011-05-27 | 2012-05-25 | MAGNESIUM HALIDE REGENERATION PRODUCT, CATALYTIC COMPONENT AND CATALYST COMPRISING SAME, AND THEIR PREPARATION |
| US13/480,866 US9068026B2 (en) | 2011-05-27 | 2012-05-25 | Magnesium halide adducts, catalyst components and catalysts comprising the same, and preparation processes thereof |
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