CN102796211B - Catalyst component for olefin polymerization and preparation method thereof, catalyst for olefin polymerization, and olefin polymerization method - Google Patents
Catalyst component for olefin polymerization and preparation method thereof, catalyst for olefin polymerization, and olefin polymerization method Download PDFInfo
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- CN102796211B CN102796211B CN201110142182.2A CN201110142182A CN102796211B CN 102796211 B CN102796211 B CN 102796211B CN 201110142182 A CN201110142182 A CN 201110142182A CN 102796211 B CN102796211 B CN 102796211B
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Abstract
The invention relates to a catalyst component for olefin polymerization and a preparation method thereof. The catalyst component contains a product obtained by reacting a magnesium halide adduct, a titanium compound and an internal electron donor compound, wherein the spherical magnesium halide adduct contains magnesium halide, alcohol except methanol, the methanol, a polyol ester compound and water or does not contain the water. The invention also relates to a catalyst which contains the catalyst component and is used for olefin polymerization, application of the catalyst to olefin polymerization reaction, and an olefin polymerization method. The catalyst for olefin polymerization has a smooth particle surface, a regular shape, high breaking resistance in the polymerization process, and high hydrogen regulation sensitivity in the olefin polymerization reaction.
Description
Technical field
The present invention relates to a kind of catalyst component for olefinic polymerization, be somebody's turn to do the preparation method for the catalyst component of olefinic polymerization, the catalyst component for olefinic polymerization of being prepared by the method, the described catalyst component for olefinic polymerization is in the application of the catalyzer for olefinic polymerization, for a catalyzer for olefinic polymerization, this catalyzer for olefinic polymerization is at application and the olefine polymerizing process of olefinic polyreaction.
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.Conventionally, described magnesium halide in active adopts the adducts of magnesium halide and alcohol, after reacting, obtains spherical catalyst using it as carrier with halogenated titanium and electron donor compound.When this spherical catalyst is used for to olefinic polymerization (particularly propylene polymerization), have higher polymerization activity and vertical structure directional property, resulting polymkeric substance has good particle form.
The adducts of published magnesium halide and alcohol, generally includes magnesium chloride and alcohol binary composition.In some published alcohol adduct, also comprise a small amount of water.This type of alcohol adduct can be dry by spraying, spray cooling, high pressure is extruded or prepared by the method such as high-speed stirring.As: the disclosed magnesium chloride alcohol adduct of US4421674, US4469648, WO8707620, WO9311166, US5100849, US6020279, US4399054, EP0395383, US6127304 and US6323152.Catalyzer prepared by above-mentioned magnesium chloride alcohol adduct during for olefinic polymerization, is easy to occur the Fragmentation Phenomena of polymkeric substance, thereby causes fine polymer powder more.Its major cause may be that the catalyst active center forming on adducts carrier is inhomogeneous 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, for example: in CN1397568A and CN1563112A technology, the known internal electron donor of the industry is introduced in carrier synthetic as phthalate compound, form the spherical carrier of " magnesium dichloride-alcohol-phthalic ester " mixture, then this carrier and titanium tetrachloride reaction are formed to catalyzer.Disclosed ball type carrier is of a size of D50:70-200, and its catalyzer is for propylene polymerization, and polymerization activity is lower, is 406gPP/gcat.At CN101050245A, disclose a kind of adduct of magnesium halides, its general formula is MgX
2-mROH-nE-pH2O, wherein, E is two-oxyl hydrocarbon compounds, R is C
1-C
12alkyl, C
3-C
10cycloalkyl or C
6-C
10aryl, m is 1-5, and n is 0.005-1.0, and p is 0-0.8; The preparation method of this adduct of magnesium halides comprises: (1) is in airtight reactor, by magnesium halide, alcohol, two-oxyl hydrocarbon compounds and optionally inert media mixing, under agitation mixture is heated to 100-140 ℃, 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 adduct of magnesium halides particle, the temperature of heat-eliminating medium is controlled at-40 ℃-0 ℃.Yet, there is a large amount of irregular particles in the adduct of magnesium halides of preparing according to the method for this patent application, as needle-shaped particle, clavate particle, use this adduct of magnesium halides during for olefinic polymerization, can cause undoubtedly resulting polymers also to have a large amount of irregular particles as the catalyzer of carrier.
Summary of the invention
First object of the present invention is to overcome the above-mentioned defect that adopts the olefin polymerization catalysis that existing adduct of magnesium halides prepared as support of the catalyst, and a kind of new catalyst component for olefinic polymerization is provided.
Second object of the present invention is to provide this for the preparation method of the catalyst component of olefinic polymerization.
The 3rd object of the present invention is to provide the catalyst component for olefinic polymerization that adopts above-mentioned preparation method to prepare.
The 4th object of the present invention is to provide above-mentioned catalyst component, the application in the catalyzer for the preparation of olefinic polymerization.
The 5th object of the present invention is to provide a kind of catalyzer for olefinic polymerization.
The 6th object of the present invention is to provide the above-mentioned catalyzer for olefinic polymerization in the application of olefinic polyreaction.
The 7th object of the present invention is to provide a kind of olefine polymerizing process.
The invention provides a kind of catalyst component for olefinic polymerization, this catalyst component contains the product being obtained by spherical adduct of magnesium halides, titanium compound and the reaction of internal electron donor compound, wherein, described spherical adduct of magnesium halides contains the compound that general formula is MgXY, compound, methyl alcohol and the 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 the C of respectively do for oneself halogen, replacement or unsubstituted straight or branched
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 the C of respectively do for oneself hydrogen, halogen, replacement or unsubstituted straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl, C
2-C
20alkylene, C
2-C
20ester group, contain heteroatomic C
1-C
20alkyl, contain heteroatomic C
3-C
20cycloalkyl, contain heteroatomic C
6-C
20aryl, contain heteroatomic C
7-C
20aralkyl, contain 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, the integer that k is 0-10.
The present invention also provides the preparation method of the above-mentioned catalyst component for olefinic polymerization, the method comprises the following steps: the compound that the compound that (1) is MgXY by general formula and general formula are ROH and optional inert liquid medium mix, under agitation the mixture obtaining is heated to form the melt of 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) make described spherical solid particulate and Propanal dimethyl acetal contact reacts in inert dispersion medium; (4) by products therefrom and DOE contact reacts in inert dispersion medium after step (3) contact, obtain spherical adduct of magnesium halides, DOE is the polyol ester shown in general formula (I):
In general formula (I), R
1and R
2identical or different, and the C of respectively do for oneself halogen, replacement or unsubstituted straight or branched
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 the C of respectively do for oneself hydrogen, halogen, replacement or unsubstituted straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl, C
2-C
20alkylene, C
2-C
20ester group, contain heteroatomic C
1-C
20alkyl, contain heteroatomic C
3-C
20cycloalkyl, contain heteroatomic C
6-C
20aryl, contain heteroatomic C
7-C
20aralkyl, contain 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, the integer that k is 0-10; And (5) react described spherical adduct of magnesium halides with titanium compound, and add internal electron donor compound in the one or more time periods in before and after, during the reacting of described spherical adduct of magnesium halides and titanium compound.
The present invention also provides the catalyst component for olefinic polymerization of being prepared by above-mentioned preparation method.
The present invention also provides the application of the described catalyst component for olefinic polymerization at the catalyzer for olefinic polymerization.
The present invention also provides a kind of catalyzer for olefinic polymerization, and this catalyzer contains: (1) described catalyst component for olefinic polymerization provided by the invention; (2) alkylaluminium cpd; And (3) optional external donor compound.
The present invention also provides the application of the described catalyzer for olefinic polymerization at olefinic polyreaction.
The present invention also provides a kind of olefine polymerizing process, and the method comprises: under olefinic polymerization condition, one or more alkene are contacted with catalyzer, wherein, described catalyzer is the described catalyzer for olefinic polymerization provided by the invention.
Good according to the particle form of the described catalyst component for olefinic polymerization provided by the invention, smooth surface, good fluidity, and use when comprising this olefin polymerization catalysis for the catalyst component of olefinic polymerization and carrying out olefinic polymerization, good hydrogen response there is.
Accompanying drawing explanation
Fig. 1 represents the optical microscope photograph of the spherical 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 the optical microscope photograph of the catalyst component particle for olefinic polymerization of preparation in embodiment 1.
Embodiment
According to a first aspect of the invention, the invention provides a kind of catalyst component for olefinic polymerization, this catalyst component contains the product that spherical adduct of magnesium halides, titanium compound and the reaction of internal electron donor compound obtain, wherein, described spherical adduct of magnesium halides contains the compound that general formula is MgXY, compound, methyl alcohol and the DOE that general formula is ROH, 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, replacement 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 [] be shown with k carbon atom successively key connect, and each carbon atom also replaces base keies and connects 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, replacement 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, contain heteroatomic C
1-C
20alkyl, contain heteroatomic C
3-C
20cycloalkyl, contain heteroatomic C
6-C
20aryl, contain heteroatomic C
7-C
20aralkyl, contain 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 when k=0, 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 for example selected from a kind of 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 for example selected from a kind of 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 for example selected from a kind of 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, contain heteroatomic C
1-C
20alkyl, contain heteroatomic C
3-C
20cycloalkyl, contain heteroatomic C
6-C
20aryl, contain heteroatomic C
7-C
20aralkyl, contain 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 for example selected from a kind of 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 for example selected from a kind of 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 for example selected from a kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or the tertiary butyl.
In the present invention, described binary alcohol esters can be for example 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 esters, 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-pentanediol dibenzoate, 3-butyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol dibenzoate, 2,4-pentanediol two (Chlorodracylic acid) ester, 2,4-pentanediol two (m-chlorobenzoic acid) ester, 2,4-pentanediol two (parabromobenzoic acid) ester, 2,4-pentanediol two (o-bromobenzoic acid) ester, 2,4-pentanediol two (p-methylbenzoic acid) ester, 2,4-pentanediol two (p-tert-butyl benzoic acid) ester, 2,4-pentanediol two (to butylbenzoic acid) ester, 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-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol phenylformic acid laurate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2-allyl group-1,3-pentanediol dibenzoate, 2-methyl isophthalic acid, 3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-propyl group-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 1,3-pentanediol two (Chlorodracylic acid) ester, 1,3-pentanediol two (m-chlorobenzoic acid) ester, 1,3-pentanediol two (parabromobenzoic acid) ester, 1,3-pentanediol two (o-bromobenzoic acid) ester, 1,3-pentanediol two (p-methylbenzoic acid) ester, 1,3-pentanediol two (p-tert-butyl benzoic acid) ester, 1,3-pentanediol two (to butylbenzoic acid) ester, 1,3-pentanediol phenylformic acid laurate, 1,3-pentanediol, two laurates, 1,3-pentanediol dipropionate, 2,2,4-trimethylammonium-1,3-pentanediol di-isopropyl manthanoate, 1-trifluoromethyl-3-methyl-2,4-pentanediol dibenzoate, two pairs of fluoro methyl benzoic acid esters of 2,4-pentanediol, 2,4-pentanediol two (2-furancarboxylic acid) ester, 2-methyl-6-heptene-2,4-heptanediol dibenzoate, 3-methyl-6-heptene-2,4-heptanediol dibenzoate, 4-methyl-6-heptene-2,4-heptanediol dibenzoate, 5-methyl-6-heptene-2,4-heptanediol dibenzoate, 6-methyl-6-heptene-2,4-heptanediol dibenzoate, 3-ethyl-6-heptene-2,4-heptanediol dibenzoate, 4-ethyl-6-heptene-2,4-heptanediol dibenzoate, 5-ethyl-6-heptene-2,4-heptanediol dibenzoate, 6-ethyl-6-heptene-2,4-heptanediol dibenzoate, 3-propyl group-6-heptene-2,4-heptanediol dibenzoate, 4-propyl group-6-heptene-2,4-heptanediol dibenzoate, 5-propyl group-6-heptene-2,4-heptanediol dibenzoate, 6-propyl group-6-heptene-2,4-heptanediol dibenzoate, 3-butyl-6-heptene-2,4-heptanediol dibenzoate, 4-butyl-6-heptene-2,4-heptanediol dibenzoate, 5-butyl-6-heptene-2,4-heptanediol dibenzoate, 6-butyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dimethyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-diethyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dipropyl-6-heptene-2,4-heptanediol dibenzoate, 3,5-dibutyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dimethyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-diethyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dipropyl-6-heptene-2,4-heptanediol dibenzoate, 3,3-dibutyl-6-heptene-2,4-heptanediol dibenzoate, 3-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 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 (the Chinese cassia tree carboxyl methyl) fluorenes of 9,9-, 9-(benzoyloxy methyl)-9-(the third carboxyl methyl) fluorenes, two (the third carboxyl methyl) fluorenes of 9,9-, 9, two (the propylene carboxyl methyl) fluorenes and 9 of 9-, one or more in two (the neo-pentyl carboxyl methyl) fluorenes of 9-, cited binary alcohol esters can be commercially available, and also can adopt method well known in the art (as the method described in reference to CN1169845C) synthetic.
According to one embodiment of the present invention, the general formula of described spherical adduct of magnesium halides can be expressed as MgXY-mROH-nCH
3oH-tDOE-qH
2o, wherein, in MgXY, X is halogen, 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, and n is 0.1-1.0, and t is 0.0001-0.1, and 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, and n is 0.3-0.8, and t is 0.0002-0.01, and q is 0-0.5.
In the present invention, in formula M gXY, X and Y are 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 for example methyl, ethyl, propyl group, sec.-propyl, butyl or isobutyl-, described C
1-C
6alkoxyl group can be for example methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy or isobutoxy, described C
6-C
12aryl for example can be for phenyl, o-tolyl, a tolyl, p-methylphenyl, adjacent ethylbenzene, an ethylbenzene, to ethylbenzene or naphthyl, described C
6-C
12aryloxy can be for example phenoxy group or naphthyloxy.
Under further preferable case, the compound that general formula is MgXY can be one or more in magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination butoxy magnesium.
In the present invention, the compound that general formula is ROH refers to the alcohol 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 for example 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 for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.Described C
6-C
10aryl for example can be for phenyl, o-tolyl, a tolyl, p-methylphenyl, adjacent ethylbenzene, an ethylbenzene, to ethylbenzene or naphthyl.
Under further preferable case, the compound that general formula is ROH can be one or more in ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, n-hexyl alcohol, n-Octanol and 2-Ethylhexyl Alcohol.
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 μ m, is preferably 20-80 μ m.In this preferred implementation, the olefin polymerization catalysis being formed as support of the catalyst by this adduct of magnesium halides has good resistance to crushing performance and hydrogen response.In the present invention, the average particulate diameter of spheroidal particle can adopt Mastersizer 2000 laser particle analyzers to record.
In the present invention, at the described catalyst component for olefinic polymerization, the weight ratio of titanium elements, magnesium elements and internal electron donor compound can be 1: 5-15: 2-15, is preferably 1: 6-13: 3-12.
In the present invention, there is no particular limitation for the catalytic condition of described spherical adduct of magnesium halides and halogenated titanium, and under preferable case, described catalytic condition can comprise: temperature of reaction is 80-130 ℃, and the reaction times is 0.5-10 hour.
In the present invention, described halogenated titanium can be for preparing the conventional various halogenated titaniums that use in the process of olefin polymerization catalysis.Conventionally, described titanium compound can be for example Ti (OR ') for general formula
3-az
aand/or Ti (OR ')
4-bz
bcompound, wherein, R ' is C
1-C
20alkyl, Z is halogen, the integer that a is 1-3, the integer that b is 1-4.Under preferable case, described titanium compound is one or more in titanium tetrachloride, titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, three butoxy titanium chlorides, dibutoxy titanium dichloride, butoxy titanous chloride, triethoxy titanium chloride, diethoxy titanium dichloride, oxyethyl group titanous chloride and titanous chloride, more preferably titanium tetrachloride and/or titanium tetrabromide.
In the present invention, described internal electron donor compound can be for preparing the conventional various internal electron donor compounds that use in the process of olefin polymerization catalysis, can be for example one or more in carboxylicesters, alcohol ester, ether, ketone, amine and silane, be preferably one or more in binary alcohol esters and binary ether.
Described monobasic or polyhydric aliphatic carboxylicesters can be for example diethyl malonate, butyl ethyl malonate, 2, 3-di-isopropyl ethyl succinate, 2, 3-di-isopropyl di-iso-octyl succinate, 2, 3-di-isopropyl dibutyl succinate, 2, 3-di-isopropyl succsinic acid dimethyl esters, 2, 2-dimethyl succinate diisobutyl ester, 2-Ethyl-2-Methyl di-iso-octyl succinate, 2-Ethyl-2-Methyl ethyl succinate, diethylene adipate, Polycizer W 260, ethyl sebacate, Uniflex DBS, diethyl maleate, maleic acid n-butyl, one or more in naphthalene dicarboxylic acids diethyl ester and naphthalene dicarboxylic acids dibutylester.
Described monobasic or polynary aromatic carboxylic acid esters can be for example one or more in ethyl benzoate, phthalic ester diethyl ester, phthalic ester diisobutyl ester, phthalic ester di-n-butyl, phthalic ester di-isooctyl, phthalic ester di-n-octyl, triethyl trimellitate, tributyl trimellitate, benzene-1,2,3-tricarboxylic acid triethyl, benzene-1,2,3-tricarboxylic acid tri-n-butyl, pyromellitic acid tetra-ethyl ester and pyromellitic acid four butyl esters.
In the present invention, described binary alcohol esters is as shown in general formula (II).
Described binary ether can be as shown in general formula (III) compound:
Wherein, R
vIIand R
vIIIcan be identical or different, and can be the C of straight chain or straight chain separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl or C
7-C
20aralkyl; R
i-R
vIcan be for identical or different, and can be the C of hydrogen, halogen, straight chain or straight chain separately
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl or R
i-R
vIin the ring structure that forms of two or more bondings.In the preferred case, R
vIIand R
vIIIidentical or different, and the C of respectively do for oneself straight chain or straight chain
1-C
10alkyl; R
i, R
iI, R
vand R
vIbe hydrogen; R
iIIand R
iVidentical or different, and the C of respectively do for oneself straight chain or straight chain
1-C
18alkyl, C
3-C
18cycloalkyl, C
6-C
18aryl, C
7-C
18aralkyl or R
iIIand R
iVthe ring structure that bonding forms mutually.
In the present invention, described binary ether can be for example 2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-butyl-1,3-Propanal dimethyl acetal, 2-sec-butyl-1,3-Propanal dimethyl acetal, 2-cyclohexyl-1,3-Propanal dimethyl acetal, 2-phenyl-1,3-Propanal dimethyl acetal, 2-(2-phenylethyl)-1,3-Propanal dimethyl acetal, 2-(2-cyclohexyl ethyl)-1,3-Propanal dimethyl acetal, 2-(p-chloro-phenyl-)-1,3-Propanal dimethyl acetal, 2-(diphenyl methyl)-1,3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1,3-Propanal dimethyl acetal, 2,2-, bis-cyclopentyl-1,3-Propanal dimethyl acetal, 2,2-diethyl-1,3-Propanal dimethyl acetal, 2,2-dipropyl-1,3-Propanal dimethyl acetal, 2,2-di-isopropyl-1,3-Propanal dimethyl acetal, 2,2-dibutyl-1,3-Propanal dimethyl acetal, 2-methyl-2-propyl-1,3-Propanal dimethyl acetal, 2-methyl-2-benzyl-1,3-Propanal dimethyl acetal, 2-methyl-2-ethyl-1,3-Propanal dimethyl acetal, 2-methyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-methyl-2-phenyl-1,3-Propanal dimethyl acetal, 2-methyl-2-cyclohexyl-1,3-Propanal dimethyl acetal, two (the 2-cyclohexyl ethyls)-1 of 2,2-, 3-Propanal dimethyl acetal, 2-methyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-methyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2,2-phenylbenzene-1,3-Propanal dimethyl acetal, 2,2-dibenzyl-1,3-Propanal dimethyl acetal, two (cyclohexyl methyl)-1 of 2,2-, 3-Propanal dimethyl acetal, 2-isobutyl--2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-(1-methyl butyl)-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-phenyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-phenyl-2-the second month in a season-butyl-1,3-Propanal dimethyl acetal, 2-benzyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-cyclopentyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-cyclopentyl-2-the second month in a season-butyl-1,3-Propanal dimethyl acetal, 2-cyclohexyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-cyclohexyl-2-the second month in a season-butyl-1,3-Propanal dimethyl acetal, 2-cyclohexyl-2-cyclohexyl methyl-1, one or more in 3-Propanal dimethyl acetal and 9,9-dimethoxy-methyl fluorenes, are preferably 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal and/or 9,9-dimethoxy-methyl fluorenes.
According to the described catalyst component for olefinic polymerization provided by the invention, the preparation method of described spherical adduct of magnesium halides can comprise the following steps: the compound that the compound that (1) is MgXY by general formula and general formula are ROH and optional inert liquid medium mix, and under agitation the mixture obtaining is heated to form the melt of adduct of magnesium halides; (2) melt of described adduct of magnesium halides is added in heat-eliminating medium after shearing dissemination, form spherical solid particulate; (3) make described spherical solid particulate and Propanal dimethyl acetal contact reacts in inert dispersion medium; And (4) are by products therefrom and DOE contact reacts in inert dispersion medium after step (3) contact.Wherein, described MgXY, ROH are all identical with above-mentioned definition with DOE, and therefore not to repeat here.
In the preparation process of described spherical adduct of magnesium halides, in above-mentioned steps (1), the add-on of the compound that the compound that general formula is MgXY and general formula are ROH can suitably be selected according to the proportioning of each component in the spherical adduct of magnesium halides going for.Under preferable case, the mol ratio of the add-on of the compound that the compound that general formula is MgXY and general formula are ROH is 1: 1-8, is preferably 1: 2-6.Described general formula be the compound of MgXY and compound that general formula is ROH with describe above identical.
In the preparation process of described spherical adduct of magnesium halides, in above-mentioned steps (1), the object of described heating is in order to make magnesium halide, alcohol and inert liquid medium form the adducts melt of magnesium halide and alcohol.The condition of described heating does not have concrete restriction, can determine according to the concrete halogenated magnesium compound using.Described heating condition can comprise conventionally: Heating temperature is more than 80 ℃, and be more than 1 hour heat-up time.Under preferable case, described heating condition comprises: Heating temperature is 100-140 ℃, and be 1-5 hour heat-up time.
In the preparation process of described spherical adduct of magnesium halides, can there is not chemically interactive liquid medium with spherical adduct of magnesium halides for conventional various in this area in the inert liquid medium using in step (1), for example: 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.In further 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, the MgXY in magnesium with respect to 1 mole (being the magnesium halide adding in step (1)) conventionally, and the consumption of described inert liquid medium is 0.8-10L.
In the preparation process of described spherical adduct of magnesium halides, in above-mentioned steps (2), described shearing dissemination can adopt conventional method to implement, for example: the disclosed high-speed mixing method of CN1330086C (that is, adduct of magnesium halides speed with 2000-5000 rev/min in inert liquid medium being stirred); CN1267508C is disclosed to be rotated the mixture of adduct of magnesium halides and inert liquid medium in hypergravity bed (speed of rotation can be 1000-3000 rev/min) disperses; The disclosed mixture by adduct of magnesium halides and silicone oil and white oil of CN1463990A is the speed output with 1500-8000 rev/min with mulser; US6020279 is disclosed will contain the emulsifying mixture of adduct of magnesium halides by spray method.
In the preparation process of described spherical adduct of magnesium halides, in above-mentioned steps (2), it is for the melt supercooled of adduct of magnesium halides is formed to spherical solid particulate that the melt of described adduct of magnesium halides is added in heat-eliminating medium after shearing dissemination.In the present invention, described heat-eliminating medium is preferably inert hydrocarbon solvent, and lower boiling inert hydrocarbon solvent more preferably can be for example one or more in pentane, hexane, heptane, gasoline or petrol ether.The temperature of described heat-eliminating medium can be-40 ℃ to 0 ℃, is preferably-30 ℃ to-10 ℃.
In the preparation process of described spherical adduct of magnesium halides, after described chilling and before making solid particulate and Propanal dimethyl acetal contact reacts, the preparation method of described spherical adduct of magnesium halides preferably also comprises that the solid particulate obtaining after to described chilling with inert organic solvents washs 1-10 time.Described inert organic solvents can be for example one or more in pentane, hexane, heptane, gasoline or petrol ether.
In the preparation process of described spherical adduct of magnesium halides, 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 ℃, more preferably 45-60 ℃; Reaction times is 1-5 hour, more preferably 2-4 hour; The MgXY in magnesium with respect to 1 mole (being the magnesium halide adding in step (1)), the add-on of the Propanal dimethyl acetal in step (3) is 0.1-1.5 mole, more preferably 0.2-1 mole.
According to the preparation method of described spherical adduct of magnesium halides, in step (3), described inert dispersion medium can be for example at least one in pentane, hexane and heptane.
According to the preparation method of described adduct of magnesium halides, in order to obtain the spheroidal particle of adduct of magnesium halides, described method can also comprise filters the product obtaining 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, mix in situation about contacting with polyol ester, the add-on of described polyol ester and general formula are that the mol ratio of add-on of the compound of MgXY can be 0.01-0.5, are 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 ℃, 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 the preparation method of described adduct of magnesium halides, in step (4), described inert dispersion medium can be for example at least one in pentane, hexane and heptane.
According to the preparation method of described adduct of magnesium halides, in order to obtain the spheroidal particle of adduct of magnesium halides, described method can also comprise filters the product after described contact reacts, with inert organic solvents washing 1-10 time, is then dried.Described inert organic solvents can be identical or different with above-mentioned inert organic solvents.
According to a second aspect of the invention, the present invention also provides a kind of preparation method of the catalyst component for olefinic polymerization, the method comprises the following steps: the compound that the compound that (1) is MgXY by general formula and general formula are ROH and optional inert liquid medium mix, under agitation the mixture obtaining is heated to form the melt of 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) make described spherical solid particulate and Propanal dimethyl acetal contact reacts in inert dispersion medium; (4) by products therefrom and DOE contact reacts in inert dispersion medium after step (3) contact, obtain spherical adduct of magnesium halides, DOE is the polyol ester shown in general formula (I):
In general formula (I), R
1and R
2identical or different, and the C of respectively do for oneself halogen, replacement or unsubstituted straight or branched
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 the C of respectively do for oneself hydrogen, halogen, replacement or unsubstituted straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl, C
2-C
20alkylene, C
2-C
20ester group, contain heteroatomic C
1-C
20alkyl, contain heteroatomic C
3-C
20cycloalkyl, contain heteroatomic C
6-C
20aryl, contain heteroatomic C
7-C
20aralkyl, contain 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, the integer that k is 0-10; And (5) react described spherical adduct of magnesium halides with titanium compound, and add internal electron donor compound in the one or more time periods in before and after, during the reacting of described spherical adduct of magnesium halides and titanium compound.Wherein, described MgXY, ROH, DOE, titanium compound and internal electron donor are identical with definition mentioned above; Step (1) is to implementation method and the condition of step (4), identical with the preparation process of the spherical adduct of magnesium halides of catalyst component for olefinic polymerization, and therefore not to repeat here.
Preparation method at the described catalyst component for olefinic polymerization, in step (5), the concrete operation method that described spherical adduct of magnesium halides is reacted with titanium compound preferably includes: titanium compound is cooled to 0 ℃ following (being preferably-5 to-25 ℃), then add the spherical adduct of magnesium halides obtaining in step (4), and be uniformly mixed 10-60 minute at this temperature, be warming up to afterwards temperature of reaction (i.e. about 80-130 ℃), and maintain 0.5-10 hour under this temperature of reaction.Preparation method at the described catalyst component for olefinic polymerization, described internal electron donor compound added in the one or more time periods in before and after, during the reacting of described spherical adduct of magnesium halides and titanium compound, and preferably before the reacting of described spherical adduct of magnesium halides and titanium compound, added.Described spherical adduct of magnesium halides refers to the time period afterwards and before being warming up to temperature of reaction in described spherical adduct of magnesium halides adds reactor with the previous time period of reacting of titanium compound.
Preparation method at the described catalyst component for olefinic polymerization, in step (5), in the spherical adduct of magnesium halides of magnesium elements, take the mol ratio of the halogenated titanium of titanium elements and the add-on of internal electron donor can be as 1: 20-150: 0.005-1, is preferably 1: 30-120: 0.01-0.6.
According to a third aspect of the present invention, the present invention also provides the catalyst component for olefinic polymerization of being prepared by aforesaid method.
According to a fourth aspect of the present invention, the present invention also provides the application of the described catalyst component for olefinic polymerization at the catalyzer for olefinic polymerization.
According to a fifth aspect of the present invention, the present invention also provides a kind of catalyzer for olefinic polymerization, and this catalyzer contains: (1) described catalyst component for olefinic polymerization provided by the invention; (2) alkylaluminium cpd; And (3) optional external donor compound.
Composition and the preparation method of the described catalyst component for olefinic polymerization are described in detail in the preceding article, do not repeat them here.
Catalyzer for olefinic polymerization according to the present invention has been used the catalyst component for olefinic polymerization according to the present invention, therefore the catalyzer for olefinic polymerization according to the present invention is when the catalyzer as olefinic polyreaction, not only demonstrate higher polymerization activity, and there is excellent hydrogen response and high stereotaxis ability, and can prepare the polymkeric substance that particle shape is good.Therefore, the catalyzer for olefinic polymerization according to the present invention is all not particularly limited for kind and the consumption of alkylaluminium cpd and external donor compound.
Described alkylaluminium cpd can be the conventional various alkylaluminium cpds in this area.For example, described alkylaluminium cpd can be one or more in triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminium, a chlorine di-n-hexyl aluminium, dichloro one aluminium triethyl, dichloro one aluminium isobutyl, dichloro one n-butylaluminum and dichloro one n-hexyl aluminium.
Described external donor compound can be the various external donor compounds that this area is conventional, and for example, described external electron donor can be one or more in carboxylic acid, acid anhydrides, ester, ketone, ether, alcohol, organo phosphorous compounds and silicoorganic compound; Preferably, described external electron donor is silicoorganic compound.The example of described silicoorganic compound can for but be not limited to: Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxy silane, second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane and (1,1, the fluoro-2-propyl group of 1-tri-)-2-ethyl piperidine base dimethoxy silane and (1, the fluoro-2-propyl group of 1,1-tri-)-methyl dimethoxysilane.
At the described catalyzer for olefinic polymerization, in the described catalyst component for olefinic polymerization of titanium elements with take the mol ratio of described alkylaluminium cpd consumption of aluminium element as 1: 1-2000, be preferably 1: 10-500, more preferably 1: 20-400; Described external donor compound and the mol ratio of described alkylaluminium cpd consumption of aluminium element of take are 1: 2-200, is preferably 1: 2.5-100, more preferably 1: 10-80.
According to a sixth aspect of the invention, the present invention also provides the application of the described catalyzer for olefinic polymerization at olefinic polyreaction.
According to a seventh aspect of the present invention, the method comprises: under olefinic polymerization condition, one or more alkene are contacted with catalyzer, wherein, described catalyzer is the catalyzer for olefinic polymerization according to the present invention.
Olefine polymerizing process according to the present invention, by using the catalyzer for olefinic polymerization according to the present invention, can be prepared the polymkeric substance that particle form is good.Described olefine polymerizing process of the present invention is not particularly limited for olefinic polymerization condition and the alkene using.
Described alkene can be for example one or more in ethene, propylene, 1-butylene, 2-butylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2-butene, 1-amylene, 2-amylene, 1-hexene and vinylbenzene, is preferably one or more in ethene, propylene, 1-butylene, 2-butylene and vinylbenzene.
According to olefine polymerizing process of the present invention, described olefinic polymerization can be carried out according to the ordinary method of this area.For example, described olefinic polymerization can be mass polymerization, vapour phase polymerization or slurry polymerization.According to olefine polymerizing process of the present invention, described olefinic polymerization condition can be the normal condition of this area, and for example, polymerization temperature can be 0-150 ℃, is preferably 60-90 ℃; Polymerization pressure can be normal pressure or pressurization.
The invention will be further described by the following examples.Yet, should be understood that, these embodiment only, for description and interpretation the present invention, are not limited to the present invention.
Embodiment 1
The present embodiment is for illustrating described catalyst component for olefinic polymerization provided by the invention and preparation method thereof and for catalyzer and the application thereof of olefinic polymerization.
(1) preparation of spherical magnesium chloride adducts
In the autoclave of 300L, add the white oil of 90L, the ethanol of the magnesium chloride of the silicone oil of 90L, 9.0kg (94.7mol) and 14.5L (249.0mol), under agitation be warming up to 125 ℃, and at 125 ℃, stir 2.5 hours, then, the mixing liquid obtaining is entered in advance in the hexane that is cooled to-30 ℃ by high-gravity rotating bed, elimination liquid, and with after hexane washing five times, at 40 ℃, vacuum-drying is 2 hours, obtains the solid matter (being the alcohol adduct of magnesium chloride) of 18kg.
In the reactor of 1.6L, the hexane that adds 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) that is dissolved in the 45ml in the hexane of 180ml is added wherein, then, be warming up to 60 ℃, and at this temperature stirring reaction 3h, carry out afterwards press filtration, with hexane washing 2 times, the hexane that adds 800ml, 2 of 8ml in the hexane of 100ml will be dissolved in again, 4-pentanediol dibenzoate adds wherein, be warming up to 60 ℃, and at this temperature stirring reaction 2h, then carry out press filtration, with hexane washing 5 times, and be dried and after 4 hours, obtain spherical magnesium chloride adducts at 60 ℃.
According to complexometry, detect the Mg content in this spherical magnesium chloride adducts, according to liquid phase chromatographic analysis method, detect respectively ethanol, the methyl alcohol and 2 in this spherical magnesium chloride adducts, the content of 4-pentanediol dibenzoate, consequently, the mol ratio of the magnesium chloride in this magnesium chloride adducts, ethanol, methyl alcohol and 2,4-pentanediol dibenzoate is 1: 1.6: 0.6: 0.0005; Adopt Mastersizer 2000 laser particle analyzers (being produced by Malvern Instruments Ltd) to record, the average particulate diameter of this magnesium chloride adducts is 43 microns.
(2) for the preparation of the catalyst component of olefinic polymerization
In the glass reaction bottle of 2000ml, add the titanium tetrachloride of 500ml and be cooled to-20 ℃, the magnesium chloride adducts making in the embodiment of 40 grams 1 is added wherein, then be warming up to 110 ℃, and in temperature-rise period, add 2 of 6.5ml, 2-sec.-propyl-2-isopentyl-1 of 4-pentanediol dibenzoate and 6.5ml, 3-Propanal dimethyl acetal, elimination liquid maintain 30min at 110 ℃ after, add again afterwards titanium tetrachloride washing 2 times, finally with hexane washing 5 times, then vacuum-drying 2 hours at 40 ℃, olefin polymerization catalyst components C1 obtained.Adopt grating spectrophotometer, according to the titanium elements content in this catalyst component of spectrophotometry; According to complexometry, detect the magnesium element content in this catalyst component; According to liquid phase chromatographic analysis method, detect respectively 2 in this catalyst component, 4-pentanediol dibenzoate and 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal content, result records titanium elements in this catalyst component, magnesium elements, 2,4-pentanediol dibenzoate and 2-sec.-propyl-2-isopentyl-1, the mass ratio of 3-Propanal dimethyl acetal is 1: 4.5: 3.1: 1.2, adopt Nikon Eclipse E200 type opticmicroscope-JVC color video camera to observe this catalyst component 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, then in stream of nitrogen gas, introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of the triethyl aluminum of 1ml, hexane solution (concentration of CHMMS is 0.1mmol/ml), the anhydrous hexane of 10ml and the catalyst component C1 of 4mg of the Cyclohexyl Methyl Dimethoxysilane (CHMMS) of 0.1ml.Close autoclave, add the hydrogen (standard volume) of 2.0L and the liquid propene of 2.3L, be warming up to 70 ℃, and at this temperature, react 1 hour.
Embodiment 2
The present embodiment is for illustrating described catalyst component for olefinic polymerization provided by the invention and preparation method thereof and its application in olefinic polymerization.
According to the method for embodiment 1 prepare magnesium chloride adducts, for the preparation of the catalyst component of olefinic polymerization with carry out propylene polymerization, difference is that 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 ℃, and at this temperature, stir 2.5 hours, then, the mixing liquid obtaining is entered in advance in the hexane that is cooled to-30 ℃ to elimination liquid by high-gravity rotating bed, and wash five times with hexane, after being dried, obtain the solid matter (being the alcohol adduct of magnesium chloride) of 18kg.
(2) for the preparation of the catalyst component of olefinic polymerization
Catalyst component according to the method for embodiment 1 for the preparation of olefinic polymerization, different is that the magnesium chloride adducts that adopts comparative example 1 step (1) to prepare obtains catalyst component DC1.
(3) propylene polymerization
According to the method for embodiment 1, carry out propylene polymerization, different is the catalyst component that uses comparative example 1 step (2) to prepare.
Comparative example 2
According to the method for comparative example 1 prepare magnesium chloride adducts, for the preparation of the catalyst component of olefinic polymerization with carry out propylene polymerization, difference is that in propylene polymerization process, the add-on of hydrogen is 6.5L.
Embodiment 3
The present embodiment is for illustrating described catalyst component for olefinic polymerization provided by the invention and preparation method thereof and its application in olefinic polymerization.
(1) preparation of adduct of magnesium halides
According to the method for embodiment 1, prepare magnesium chloride adducts, difference is that the add-on of Propanal dimethyl acetal is 10ml.
According to complexometry, detect the Mg content in this spherical magnesium chloride adducts, according to liquid phase chromatographic analysis method, detect respectively ethanol, the methyl alcohol and 2 in this spherical magnesium chloride adducts, the content of 4-pentanediol dibenzoate, consequently, the mol ratio of the magnesium chloride in this magnesium chloride adducts, ethanol, methyl alcohol and 2,4-pentanediol dibenzoate is 1: 2.2: 0.2: 0.0002; Adopt Mastersizer 2000 laser particle analyzers (being produced by Malvern Instruments Ltd) to record, the average particulate diameter of this magnesium chloride adducts is 43 microns.
(2) for the preparation of the catalyst component of olefinic polymerization
Catalyst component according to the method for embodiment 1 for the preparation of olefinic polymerization, different is that the magnesium chloride adducts that adopts embodiment 3 steps (1) to prepare obtains catalyst component C2.Adopt grating spectrophotometer, according to the titanium elements content in this catalyst component of spectrophotometry; According to complexometry, detect the magnesium element content in this catalyst component; According to liquid phase chromatographic analysis method, detect respectively 2 in this catalyst component, 4-pentanediol dibenzoate and 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal content, result records titanium elements in this catalyst component, magnesium elements, 2,4-pentanediol dibenzoate and 2-sec.-propyl-2-isopentyl-1, the mass ratio of 3-Propanal dimethyl acetal is 1: 7.2: 3.6: 2.
(3) propylene polymerization
According to the method for embodiment 1, carry out propylene polymerization, different is the catalyst component that uses embodiment 3 steps (2) to prepare.
Embodiment 4
The present embodiment is for illustrating described catalyst component for olefinic polymerization provided by the invention and preparation method thereof and its application in olefinic polymerization.
According to the method for embodiment 3 prepare magnesium chloride adducts, for the preparation of the catalyst component of olefinic polymerization with carry out propylene polymerization, difference is that in propylene polymerization process, the add-on of hydrogen is 6.5L.
Test case 1
Adopt Nikon Eclipse E200 type opticmicroscope-JVC color video camera 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.
By Fig. 1 and Fig. 2, can be found out, the particle form of the magnesium chloride adducts of embodiment 1 is regular, is all spherical substantially, and particle size distribution is more concentrated, and there is no that irregular particle exists, and does not have obvious broken particle yet; And have obvious broken particle in the magnesium chloride adducts particle of comparative example 1.
Test case 2
(1) according to the method for ASTM D1238-99, detect the melting index of polymkeric substance:
(2) adopt heptane extraction process to detect polymkeric substance degree of isotacticity, the method comprises: 2 grams of dry polymer samples are placed in extractor, with the extracting of boiling heptane, after 6 hours, residuum is dried to constant weight, the polymer weight of gained (g) is degree of isotacticity with 2 ratio;
The result detecting according to aforesaid method is as shown in table 1 below.
Table 1
From the data of above-mentioned table 1, can find out that the catalyzer that the adduct of magnesium halides that adopts method of the present invention to make is prepared as support of the catalyst has good hydrogen response in propylene polymerization.Concrete, by the melting index of the polymkeric substance that adopts catalyst component C1 and C2 to carry out to obtain after propylene polymerization is compared and can be found out with the melting index of the polymkeric substance that adopts catalyst component DC1 to carry out to obtain after propylene polymerization respectively, with respect to catalyst component DC1, catalyst component C1 and C2 have good hydrogen response.
Test case 3
The polymkeric substance making in embodiment 1 and comparative example 1 is sieved, and its result is as shown in table 2 below:
Table 2
Data by upper table 2 can be found out, in preparing the process of propene polymer, the catalyzer that employing is made as support of the catalyst by described adduct of magnesium halides provided by the invention and the fine powder content less (particle size is the fine powder that is generally below 80 orders) of the propene polymer that makes, visible, the catalyzer of being made by described adduct of magnesium halides provided by the invention is difficult for broken, thereby has good resistance to crumbliness.
Below describe by reference to the accompanying drawings the preferred embodiment of the present invention in detail; 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 concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, 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 (51)
1. the catalyst component for olefinic polymerization, this catalyst component contains the product being obtained by spherical adduct of magnesium halides, titanium compound and the reaction of internal electron donor compound, it is characterized in that, described spherical adduct of magnesium halides contains the compound that general formula is MgXY, compound, methyl alcohol and the 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 the C of respectively do for oneself halogen, replacement or unsubstituted straight or branched
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 the C of respectively do for oneself hydrogen, halogen, replacement or unsubstituted straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl, C
2-C
20alkylene, C
2-C
20ester group, contain heteroatomic C
1-C
20alkyl, contain heteroatomic C
3-C
20cycloalkyl, contain heteroatomic C
6-C
20aryl, contain heteroatomic C
7-C
20aralkyl, contain 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, the integer that k is 0-10.
2. catalyst component according to claim 1, wherein, the general formula of described spherical adduct of magnesium halides is MgXY-mROH-nCH
3oH-tDOE-qH
2o, wherein, m is 1-2.4, and n is 0.1-1.0, and t is 0.0001-0.1, and q is 0-0.8.
3. catalyst component according to claim 2, wherein, m is 1.5-2.2, and n is 0.3-0.8, and t is 0.0002-0.01, and q is 0-0.5.
4. catalyst component according to claim 1 and 2, wherein, the compound that MgXY represents is one or more in magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination butoxy magnesium; The compound that ROH represents 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.
5. catalyst component according to claim 1, wherein, R in DOE shown in described general formula (I)
1and R
2halogen, C respectively do for oneself
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
2khydrogen, halogen, C respectively do for oneself
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.
6. catalyst component according to claim 5, wherein, R
1and R
2c respectively does for oneself
1-C
6alkyl, C
3-C
6cycloalkyl, C
6-C
8aryl or C
7-C
8aralkyl; R
3-R
6hydrogen, C respectively do for oneself
1-C
6alkyl or C
3-C
6cycloalkyl; R
1-R
2khydrogen or C respectively do for oneself
1-C
4alkyl.
7. catalyst component according to claim 1 and 2, wherein, described DOE is the binary alcohol esters shown in general formula (II):
In general formula (II), R
1and R
2identical with the definition in general formula (I); R
3'-R
6', R
7and R
8identical or different, and the C of respectively do for oneself hydrogen, halogen, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl, C
2-C
20alkylene, contain heteroatomic C
1-C
20alkyl, contain heteroatomic C
3-C
20cycloalkyl, contain heteroatomic C
6-C
20aryl, contain heteroatomic C
7-C
20aralkyl, contain 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 is one or more in halogen, nitrogen, oxygen, sulphur, silicon and phosphorus.
8. catalyst component according to claim 7, wherein, R
1and R
2halogen, C respectively do for oneself
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
8hydrogen, halogen, C respectively do for oneself
1-C
12alkyl, C
3-C
12cycloalkyl, C
6-C
12aryl, C
7-C
12aralkyl or C
2-C
12alkylene.
9. catalyst component according to claim 8, wherein, R
1and R
2c respectively does for oneself
1-C
6alkyl, C
3-C
6cycloalkyl, C
6-C
8aryl or C
7-C
8aralkyl; R
3'-R
6' hydrogen, C respectively do for oneself
1-C
6alkyl or C
3-C
6cycloalkyl; R
7-R
8identical or different, hydrogen or C respectively do for oneself
1-C
4alkyl.
10. catalyst component according to claim 1, wherein, described spherical adduct of magnesium halides is spheroidal particle, and the average particulate diameter of this spheroidal particle is 10-100 micron.
11. catalyst components according to claim 1, wherein, described titanium compound is general formula Ti (OR ')
3-az
aand/or Ti (OR ')
4-bz
bcompound, wherein, R ' is C
1-C
20alkyl, Z is halogen, the integer that a is 1-3, the integer that b is 1-4.
12. catalyst components according to claim 11, wherein, described titanium compound is one or more in titanous chloride, titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, three butoxy titanium chlorides, dibutoxy titanium dichloride, butoxy titanous chloride, triethoxy titanium chloride, diethoxy titanium dichloride and oxyethyl group titanous chloride.
13. catalyst components according to claim 12, wherein, described titanium compound is titanium tetrachloride and/or titanium tetrabromide.
14. catalyst components according to claim 1, wherein, described internal electron donor compound is one or more in carboxylicesters, alcohol ester, ether, ketone, amine and silane.
15. catalyst components according to claim 14, wherein, described internal electron donor compound is one or more in binary alcohol esters and binary ether.
16. catalyst components according to claim 1, wherein, at the described catalyst component for olefinic polymerization, the weight ratio of titanium elements, magnesium elements and internal electron donor compound is 1:5-15:2-15.
17. catalyst components according to claim 16, wherein, at the described catalyst component for olefinic polymerization, the weight ratio of titanium elements, magnesium elements and internal electron donor compound is 1:6-13:3-12.
18. according to the catalyst component described in claim 1,10 or 16, and wherein, the preparation method of described spherical adduct of magnesium halides comprises the following steps:
(1) compound that is MgXY by general formula and general formula are that the compound of ROH and optional inert liquid medium mix, and under agitation the mixture obtaining are heated to form the melt of adduct of magnesium halides, and 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) make described spherical solid particulate and Propanal dimethyl acetal contact reacts in inert dispersion medium; And
(4) by products therefrom and DOE contact reacts in inert dispersion medium after step (3) contact, described DOE is the polyol ester shown in general formula (I).
19. catalyst components according to claim 18, wherein, in step (1), the temperature of described heating is 100-140 ℃, the time of described heating is 1-5 hour; General formula is that the mol ratio of the compound of MgXY and the add-on of the compound that general formula is ROH is 1:1-8; With respect to the MgXY in magnesium of 1 mole, 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.
20. catalyst components according to claim 18, wherein, in step (2), described heat-eliminating medium is inert hydrocarbon solvent; The temperature of described heat-eliminating medium is-40 ℃ to 0 ℃.
21. catalyst components according to claim 20, wherein, in step (2), 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 ℃ to-10 ℃.
22. catalyst components according to claim 18, wherein, the described catalytic condition in step (3) comprises: temperature of reaction is 40-65 ℃, and the reaction times is 1-5 hour, with respect to the MgXY in magnesium of 1 mole, the add-on of described Propanal dimethyl acetal is 0.1-1.5 mole.
23. catalyst components according to claim 22, wherein, with respect to the MgXY in magnesium of 1 mole, the add-on of described Propanal dimethyl acetal is 0.2-1.0 mole.
24. catalyst components according to claim 18, wherein, the described catalytic condition in step (4) comprises: temperature of reaction is 40-65 ℃, and the reaction times is 1-5 hour, with respect to the MgXY in magnesium of 1 mole, the add-on of described DOE is 0.01-0.5 mole.
25. catalyst components according to claim 24, wherein, with respect to the MgXY in magnesium of 1 mole, the add-on of described DOE is 0.02-0.2 mole.
26. 1 kinds of preparation methods for the catalyst component of olefinic polymerization, the method comprises the following steps:
(1) compound that is MgXY by general formula and general formula are that the compound of ROH and optional inert liquid medium mix, and under agitation the mixture obtaining are heated to form the melt of adduct of magnesium halides, and 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) make described spherical solid particulate and Propanal dimethyl acetal contact reacts in inert dispersion medium;
(4) by products therefrom and DOE contact reacts in inert dispersion medium after step (3) contact, obtain spherical adduct of magnesium halides, DOE is the polyol ester shown in general formula (I):
In general formula (I), R
1and R
2identical or different, and the C of respectively do for oneself halogen, replacement or unsubstituted straight or branched
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 the C of respectively do for oneself hydrogen, halogen, replacement or unsubstituted straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl, C
2-C
20alkylene, C
2-C
20ester group, contain heteroatomic C
1-C
20alkyl, contain heteroatomic C
3-C
20cycloalkyl, contain heteroatomic C
6-C
20aryl, contain heteroatomic C
7-C
20aralkyl, contain 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, the integer that k is 0-10; And
(5) described spherical adduct of magnesium halides is reacted with titanium compound, and add internal electron donor compound in the one or more time periods in before and after, during described spherical adduct of magnesium halides reacts with titanium compound.
27. methods according to claim 26, wherein, in step (1), the temperature of described heating is 100-140 ℃, the time of described heating is 1-5 hour; General formula is that the mol ratio of the compound of MgXY and the add-on of the compound that general formula is ROH is 1:1-8; With respect to the MgXY in magnesium of 1 mole, 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.
28. methods according to claim 26, wherein, the compound that the general formula in step (1) is MgXY is one or more in magnesium dichloride, dibrominated magnesium, phenoxy group magnesium chloride, isopropoxy magnesium chloride and butoxy magnesium chloride; General formula is that the compound of 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.
29. methods according to claim 26, wherein, in step (2), described heat-eliminating medium is inert hydrocarbon solvent; The temperature of described heat-eliminating medium is-40 ℃ to 0 ℃.
30. methods according to claim 29, wherein, in step (2), 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 ℃ to-10 ℃.
31. methods according to claim 26, wherein, the described catalytic condition in step (3) comprises: temperature of reaction is 40-65 ℃, and the reaction times is 1-5 hour, with respect to the MgXY in magnesium of 1 mole, the add-on of described Propanal dimethyl acetal is 0.1-1.5 mole.
32. methods according to claim 31, wherein, with respect to the MgXY in magnesium of 1 mole, the add-on of described Propanal dimethyl acetal is 0.2-1.0 mole.
33. methods according to claim 26, wherein, R in DOE shown in the described general formula (I) in step (4)
1and R
2halogen, C respectively do for oneself
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
2khydrogen, halogen, C respectively do for oneself
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.
34. methods according to claim 33, wherein, R
1and R
2c respectively does for oneself
1-C
6alkyl, C
3-C
6cycloalkyl, C
6-C
8aryl or C
7-C
8aralkyl; R
3-R
6hydrogen, C respectively do for oneself
1-C
6alkyl or C
3-C
6cycloalkyl; R
1-R
2khydrogen or C respectively do for oneself
1-C
4alkyl.
35. methods according to claim 26, wherein, the described DOE in step (4) is the binary alcohol esters shown in general formula (II):
In general formula (II), R
1and R
2identical with the definition in general formula (I); R
3'-R
6', R
7and R
8identical or different, and the C of respectively do for oneself hydrogen, halogen, straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl, C
2-C
20alkylene, contain heteroatomic C
1-C
20alkyl, contain heteroatomic C
3-C
20cycloalkyl, contain heteroatomic C
6-C
20aryl, contain heteroatomic C
7-C
20aralkyl, contain 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 is one or more in halogen, nitrogen, oxygen, sulphur, silicon and phosphorus.
36. methods according to claim 35, wherein, R
1and R
2halogen, C respectively do for oneself
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
8hydrogen, halogen, C respectively do for oneself
1-C
12alkyl, C
3-C
12cycloalkyl, C
6-C
12aryl, C
7-C
12aralkyl or C
2-C
12alkylene.
37. methods according to claim 36, wherein, R
1and R
2c respectively does for oneself
1-C
6alkyl, C
3-C
6cycloalkyl, C
6-C
8aryl or C
7-C
8aralkyl; R
3'-R
6' hydrogen, C respectively do for oneself
1-C
6alkyl or C
3-C
6cycloalkyl; R
7-R
8identical or different, hydrogen or C respectively do for oneself
1-C
4alkyl.
38. methods according to claim 26, wherein, the described catalytic condition in step (4) comprises: temperature of reaction is 40-65 ℃, and the reaction times is 1-5 hour, with respect to the MgXY in magnesium of 1 mole, the add-on of described DOE is 0.01-0.5 mole.
39. according to the method described in claim 38, and wherein, with respect to the MgXY in magnesium of 1 mole, the add-on of described DOE is 0.02-0.2 mole.
40. methods according to claim 26, wherein, in step (5), in the spherical adduct of magnesium halides of magnesium elements, take the mol ratio of the titanium compound of titanium elements and the add-on of internal electron donor compound as 1:20-150:0.005-1.
41. according to the method described in claim 40, wherein, and in step (5), in the spherical adduct of magnesium halides of magnesium elements, take the mol ratio of the titanium compound of titanium elements and the add-on of internal electron donor compound as 1:30-120:0.01-0.6.
42. methods according to claim 26, wherein, the described titanium compound in step (5) is general formula Ti (OR ')
3-az
aand/or Ti (OR ')
4-bz
bcompound, wherein, R ' is C
1-C
20alkyl, Z is halogen, the integer that a is 1-3, the integer that b is 1-4.
43. according to the method described in claim 42, wherein, described titanium compound is one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, three butoxy titanium chlorides, dibutoxy titanium dichloride, butoxy titanous chloride, triethoxy titanium chloride, diethoxy titanium dichloride, oxyethyl group titanous chloride and titanous chloride.
44. according to the method described in claim 43, and wherein, described titanium compound is titanium tetrachloride and/or titanium tetrabromide.
45. methods according to claim 26, wherein, the described internal electron donor compound in step (5) is one or more in carboxylicesters, alcohol ester, ether, ketone, amine and silane.
46. according to the method described in claim 45, and wherein, the described internal electron donor compound in step (5) is one or more in binary alcohol esters and binary ether.
47. catalyst components for olefinic polymerization that in claim 26-46 prepared by the method described in any one.
The catalyst component for olefinic polymerization described in 48. claims 47 is in the application of the catalyzer for olefinic polymerization.
49. 1 kinds of catalyzer for olefinic polymerization, this catalyzer contains:
(1) catalyst component for olefinic polymerization described in claim 47;
(2) alkylaluminium cpd; And
(3) optional external donor compound.
The catalyzer for olefinic polymerization described in 50. claims 49 is in the application of olefinic polyreaction.
51. 1 kinds of olefine polymerizing process, the method comprises: under olefinic polymerization condition, one or more alkene are contacted with catalyzer, it is characterized in that, described catalyzer is the catalyzer for olefinic polymerization described in claim 49.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110142182.2A CN102796211B (en) | 2011-05-27 | 2011-05-27 | Catalyst component for olefin polymerization and preparation method thereof, catalyst for olefin polymerization, and olefin polymerization method |
| 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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| CN1958619A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Adduct of round magnesium halides, preparation method and application |
| CN101724102A (en) * | 2008-10-24 | 2010-06-09 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst thereof |
| WO2011006278A1 (en) * | 2009-07-15 | 2011-01-20 | China Petroleum & Chemical Corporation | Spherical magnesium halide adduct, catalyst component and catalyst for olefin polymerization prepared therefrom |
| CN102040690A (en) * | 2009-10-20 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing polypropylene with low ash content |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958619A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Adduct of round magnesium halides, preparation method and application |
| CN101724102A (en) * | 2008-10-24 | 2010-06-09 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst thereof |
| WO2011006278A1 (en) * | 2009-07-15 | 2011-01-20 | China Petroleum & Chemical Corporation | Spherical magnesium halide adduct, catalyst component and catalyst for olefin polymerization prepared therefrom |
| CN102040690A (en) * | 2009-10-20 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing polypropylene with low ash content |
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