CN102796208B - 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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- CN102796208B CN102796208B CN201110142021.3A CN201110142021A CN102796208B CN 102796208 B CN102796208 B CN 102796208B CN 201110142021 A CN201110142021 A CN 201110142021A CN 102796208 B CN102796208 B CN 102796208B
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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 spherical 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 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, this is used for the preparation method of 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 is used for the catalyzer of olefinic polymerization 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, sets it as after carrier reacts with titanium compound and electron donor compound and obtains spherical catalyst.When this spherical catalyst is used for to olefinic polymerization (particularly propylene polymerization), have higher polymerization activity and vertical structure directional property, the polymkeric substance obtaining has good particle form.
The adducts of own disclosed 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 are extruded or the method preparation 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 titanium compound 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, known industry internal electron donor 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.Disclose a kind of adduct of magnesium halides at CN101050245A, its general formula is MgX
2-mROH-nE-pH
2o, 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 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 adduct of magnesium halides particle, the temperature of heat-eliminating medium is controlled at-40 DEG C-0 DEG C.But, 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 catalyzer for olefinic polymerization prepared as support of the catalyst of existing adduct of magnesium halides, and a kind of new catalyst component for olefinic polymerization is provided.
Second object of the present invention is to provide this preparation method for 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 the application of the described catalyst component for olefinic polymerization at the catalyzer for 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 application of the described catalyzer for olefinic polymerization at 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 spherical adduct of magnesium halides, titanium compound and internal electron donor compound and reacts the product obtaining, wherein, described spherical adduct of magnesium halides contains the compound that general formula is MgXY, compound and the methyl alcohol 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.
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, an X is halogen, and another X 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, obtain spherical adduct of magnesium halides; And (4) react described spherical adduct of magnesium halides with titanium compound, and add internal electron donor compound in 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 aforesaid 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 the catalyzer for olefinic polymerization that comprises this catalyst component for olefinic polymerization while carrying out olefinic polymerization, there is good hydrogen response.
Brief description of the drawings
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 spherical adduct of magnesium halides, titanium compound and internal electron donor compound is reacted to the product obtaining, wherein, described spherical adduct of magnesium halides contains the compound that general formula is MgXY, compound and the methyl alcohol 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.
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-qH
2o, wherein, in MgXY, X is halogen, 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; M is 1-2.4, and n is 0.1-1.5, and q is 0-0.8.
In the preferred case, in the general formula of above-mentioned spherical adduct of magnesium halides, m is 1.3-2.2, and n is 0.3-1.2, and q is 0-0.5.
In described spherical adduct of magnesium halides, the compound that general formula is MgXY refers to magnesium halide.In the preferred case, in formula M gXY, X is halogen, and Y is 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 can be for example 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 is one or more in magnesium dichloride, dibrominated magnesium, phenoxy group magnesium chloride, isopropoxy magnesium chloride and butoxy magnesium chloride.
In described spherical adduct of magnesium halides, 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 can be for example 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 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.
According to one embodiment of the present invention, described spherical adduct of magnesium halides can also contain or not contain o-hydroxybenzoate and/or polyol ester.In this case, described spherical adduct of magnesium halides can be by formula M gXY-mROH-nCH
3oH-sG-tDOE-qH
2o represents, wherein, MgXY, ROH, m, n and q are all identical with above-mentioned definition, and G represents o-hydroxybenzoate, and s is 0-0.05, and DOE represents polyol ester, and t is 0-0.1.In the time that s and t are 0 (being containing o-hydroxybenzoate and polyol ester in described spherical adduct of magnesium halides), formula M gXY-mROH-nCH
3oH-sG-tDOE-qH
2o is equal to formula M gXY-mROH-nCH
3oH-qH
2o; When t is 0, but when s is not 0 (be to contain o-hydroxybenzoate in described spherical adduct of magnesium halides, but not containing polyol ester), formula M gXY-mROH-nCH
3oH-sG-tDOE-qH
2o is equal to formula M gXY-mROH-nCH
3oH-sG-qH
2o; When s is 0, but when t is not 0 (be to contain polyol ester in described spherical adduct of magnesium halides, but not containing o-hydroxybenzoate), formula M gXY-mROH-nCH
3oH-sG-tDOE-qH
2o is equal to formula M gXY-mROH-nCH
3oH-tDOE-qH
2o; In the time that s and t are all not 0, described spherical adduct of magnesium halides contains o-hydroxybenzoate and polyol ester.
In the preferred case, described spherical adduct of magnesium halides also contains o-hydroxybenzoate and/or polyol ester.In this preferred implementation, the particle form of described spherical adduct of magnesium halides is good, make the catalyzer for olefinic polymerization that comprises this spherical adduct of magnesium halides there is good particle form, and this catalyzer have good resistance to crumbliness in olefinic polyreaction.
In the situation that described spherical adduct of magnesium halides contains o-hydroxybenzoate, the general formula of described spherical adduct of magnesium halides can be expressed as: MgXY-mROH-nCH
3oH-sG-qH
2o, wherein, MgXY, ROH, m and q are all identical with above-mentioned definition; G represents described o-hydroxybenzoate, and s is 0.001-0.05, is preferably 0.002-0.04; N is 0.1-1, is preferably 0.3-0.7.
Described o-hydroxybenzoate can be represented by following formula (1):
Wherein, R
1for C
1-C
12straight or branched alkyl, C
3-C
10cycloalkyl, C
6-C
10aryl or C
7-C
10aralkyl.Described C
1-C
12straight or branched alkyl can be for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, isopentyl, hexyl or isohexyl, described C
3-C
10cycloalkyl can be for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, described C
6-C
10aryl can be for example phenyl, o-tolyl, a tolyl, p-methylphenyl, adjacent ethylbenzene, an ethylbenzene, to ethylbenzene or naphthyl, described C
7-C
10aralkyl can be for example indenyl, benzyl or phenylethyl.Under further preferable case, described o-hydroxybenzoate is one or more in Methyl Salicylate, salicylic acid ethyl ester, salicylic acid n-propyl, salicylic acid isopropyl ester, the positive butyl ester of salicylic acid and isobutyl o-hydroxybenzoate.
In the situation that described spherical adduct of magnesium halides contains polyol ester, the general formula of described spherical adduct of magnesium halides can be expressed as: MgXY-mROH-nCH
3oH-tDOE-qH
2o, wherein, MgXY, ROH, m and q are all identical with above-mentioned definition; DOE represents described polyol ester, and t is 0.0001-0.1, is preferably 0.0002-0.01; N is 0.1-1, is preferably 0.3-0.8.
Described polyol ester can be represented by following formula (2):
Wherein, R
2and R
3can 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 (2), 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, be i.e. total k carbon atom and R in bracket
1, R
2, R
3... R
2kdeng 2k substituting group, R
4-R
7and 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
4-R
7and 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 in the time of k=0, in the polyol ester shown in formula (2), substituting group is R
4, R
5carbon atom directly and substituting group be R
6, R
7carbon atom key connect.
In the preferred case, described polyol ester is binary alcohol esters, and described binary alcohol esters can be represented by following formula (3):
Wherein, R
2and R
3identical with the definition in above-mentioned formula (2); R
4'-R
7', R
8and R
9can be identical 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
4'-R
7' and R
8-R
9in 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.
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, 2,4-pentanediol two is to fluoro methyl benzoic acid ester, 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-celebrates alkene-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-, one or more in two (the propylene carboxyl methyl) fluorenes of 9,9-and two (the neo-pentyl carboxyl methyl) fluorenes of 9,9-, cited part binary alcohol esters can be commercially available, and other can be synthetic with reference to the method described in CN1436796A.
In the preferred embodiment of the present invention, the average particulate diameter of described spherical adduct of magnesium halides can be 10-100 μ m, is preferably 20-80 μ m.In this preferred implementation, the catalyzer for olefinic polymerization that comprises this spherical adduct of magnesium halides has good resistance to crumbliness 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 condition of the reaction of described spherical adduct of magnesium halides, titanium compound and internal electron donor compound, under preferable case, the condition of this reaction can comprise: temperature of reaction is 80-130 DEG C, and the reaction times is 0.5-10 hour.
In the present invention, described titanium compound can be for the preparation of the conventional various titanium compounds that use in the process of the catalyzer of olefinic polymerization.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 F, Cl, Br or I, 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.
In the present invention, described internal electron donor compound can be for the preparation of the conventional various internal electron donor compounds that use in the process of the catalyzer of olefinic polymerization, can be for example one or more in carboxylicesters, alcohol ester, ether, ketone, amine and silane, be preferably one or more in monobasic or polyhydric aliphatic family carboxylicesters, monobasic or polynary aromatic carboxylic acid esters, 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.
Described binary alcohol esters can be the compound being represented by following formula (4),
Wherein, R
14and R
15can 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 (4), the contents table of bracket [] be shown with d carbon atom successively key connect, and each carbon atom also replaces base keies and connects with 2, be i.e. total d carbon atom and R in bracket
1, R
2, R
3... R
2ddeng 2d substituting group, R
10-R
13and R
1-R
2didentical 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, 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
10-R
13and R
1-R
2din 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, d is the integer of 0-10, and in the time of d=0, in the binary alcohol esters shown in formula (4), substituting group is R
10, R
11carbon atom directly and substituting group be R
12, R
13carbon atom key connect.
Under preferable case, described binary alcohol esters is the compound being represented by following formula (5):
Wherein, R
14and R
15identical with the definition in above-mentioned formula (4); R
10'-R
13', R
16and R
17can be identical 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
10'-R
13', R
16and R
17in 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.
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, 2,4-pentanediol two is to fluoro methyl benzoic acid ester, 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-, one or more in two (the propylene carboxyl methyl) fluorenes of 9,9-and two (the neo-pentyl carboxyl methyl) fluorenes of 9,9-, cited part binary alcohol esters can be commercially available, and other can be synthetic with reference to the method described in CN1436796A.
Described binary ether can be the compound being represented by following formula (6),
Wherein, R
18and R
19can 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
20-R
25can be 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
20-R
25in the ring structure that forms of two or more bondings.In the preferred case, R
18and R
19identical or different, and the C of respectively do for oneself straight chain or straight chain
1-C
10alkyl; R
20, R
21, R
24and R
25be hydrogen; R
22and R
23identical 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
22and R
23the 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-sec.-propyl-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.
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:
(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;
(2) melt of described adduct of magnesium halides is added in heat-eliminating medium after shearing dissemination, form spherical solid particulate; And
(3) make described spherical solid particulate and Propanal dimethyl acetal contact reacts in inert dispersion medium;
Wherein, the compound that the compound that described general formula is MgXY and general formula are ROH all with above describe identical.
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 DEG C, and be more than 1 hour heat-up time.Under preferable case, described heating condition comprises: Heating temperature is 100-140 DEG C, and be 1-5 hour heat-up time.
In the preparation process of described spherical adduct of magnesium halides, can variously not there is not chemically interactive liquid medium with spherical adduct of magnesium halides for what this area was commonly used 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 elements 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 (, adduct of magnesium halides being stirred with the speed of 2000-5000 rev/min in inert liquid medium); CN1267508C is disclosed to be rotated the mixture of adduct of magnesium halides and inert liquid medium in hypergravity bed, and (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 the adduct of magnesium halides after disperseing 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 more preferably lower boiling inert hydrocarbon solvent 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 DEG C to 0 DEG C, is preferably-30 DEG C to-10 DEG C.
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 DEG C, more preferably 45-60 DEG C; Reaction times is 1-5 hour, more preferably 2-4 hour; The MgXY in magnesium elements (being the magnesium halide adding in step (1)) with respect to 1 mole, the add-on of the Propanal dimethyl acetal in step (3) is 0.1-1.5 mole, more preferably 0.2-1 mole.Under above-mentioned preferred contact reacts condition, can further improve the particle form of the spherical adduct of magnesium halides of final preparation.
In the preparation process 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.
In the preferred case, the preparation method of described spherical adduct of magnesium halides also comprises that the spheroidal particle of the adduct of magnesium halides that process said process is obtained mixes and contacts with o-hydroxybenzoate and/or polyol ester.
In the case of the spheroidal particle of described adduct of magnesium halides and o-hydroxybenzoate are further mixed contacting, the add-on of described o-hydroxybenzoate and the mol ratio of MgXY can be 0.002-0.5, are preferably 0.02-0.2; The spheroidal particle of described adduct of magnesium halides mixes with o-hydroxybenzoate the condition contacting and can comprise: temperature is 40-65 DEG C, and the time is 1-5 hour.Described o-hydroxybenzoate is preferably the compound shown in above-mentioned formula (1).
In the case of the spheroidal particle of described adduct of magnesium halides and polyol ester are further mixed contacting, the mol ratio of the add-on of the compound that the add-on of described polyol ester and general formula are MgXY can be 0.01-0.5, is preferably 0.02-0.2; The spheroidal particle of described adduct of magnesium halides mixes with polyol ester the condition contacting and can comprise: temperature is 40-65 DEG C, and the time is 1-5 hour.Described polyol ester is preferably the polyol ester shown in above-mentioned formula (2), more preferably the binary alcohol esters shown in above-mentioned formula (3).
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, and 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, under agitation the mixture obtaining is heated to form the melt of adduct of magnesium halides, wherein, in formula M gXY, an X is halogen, and another X 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, obtain spherical adduct of magnesium halides; And
(4) described spherical adduct of magnesium halides is reacted with titanium compound, and add internal electron donor compound in one or more time periods in before and after, during the reacting of described spherical adduct of magnesium halides and titanium compound.
In the preparation method of the above-mentioned catalyst component for olefinic polymerization, step (1) to (3) is identical to (3) with the step (1) in the preparation method of spherical adduct of magnesium halides who describes above, does not repeat at this.
In the preparation method of the described catalyst component for olefinic polymerization, the described spherical adduct of magnesium halides of step (4) reacts with titanium compound and can adopt mode same as the prior art to carry out, concrete, for example, in step (4), the concrete operation method that described spherical adduct of magnesium halides is reacted with titanium compound preferably includes: titanium compound is cooled to 0 DEG C following (being preferably-5 to-25 DEG C), then add the spherical adduct of magnesium halides obtaining in step (3), and be uniformly mixed 10-60 minute at this temperature, be warming up to afterwards temperature of reaction (i.e. about 80-130 DEG C), and maintain 0.5-10 hour under this temperature of reaction.In the preparation method of 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.
In the preparation method of the described catalyst component for olefinic polymerization, in step (4), in the spherical adduct of magnesium halides of magnesium elements, can be as 1 taking the mol ratio of the titanium compound of titanium elements and the add-on of internal electron donor: 20-150: 0.005-1, is preferably 1: 30-120: 0.01-0.6.
In the preparation method of the described catalyst component for olefinic polymerization, middle titanium compound and the internal electron donor of describing is identical respectively with above with internal electron donor for described titanium compound.
In a kind of preferred implementation, before the preparation method of the described catalyst component for olefinic polymerization is also included in the spherical adduct of magnesium halides and titanium compound contact reacts that step (3) is obtained, make it mix and contact with o-hydroxybenzoate and/or polyol ester, further to improve the particle form of adduct of magnesium halides.
Described spherical adduct of magnesium halides and o-hydroxybenzoate are being mixed contact in the situation that, the add-on of described o-hydroxybenzoate and the mol ratio of MgXY can be 0.002-0.5, are preferably 0.02-0.2; The spheroidal particle of described adduct of magnesium halides mixes with o-hydroxybenzoate the condition contacting and can comprise: temperature is 40-65 DEG C, and the time is 1-5 hour.Described o-hydroxybenzoate is with the middle o-hydroxybenzoate of describing is identical above.
In the case of the spheroidal particle of described adduct of magnesium halides and polyol ester are mixed contact, the mol ratio of the add-on of the compound that the add-on of described polyol ester and general formula are MgXY can be 0.01-0.5, be preferably 0.02-0.2; The spheroidal particle of described adduct of magnesium halides mixes with polyol ester the condition contacting and can comprise: temperature is 40-65 DEG C, and the time is 1-5 hour.Described polyol ester is with the middle polyol ester of describing is identical above.
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) the 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 used the catalyst component for olefinic polymerization according to the present invention, therefore the catalyzer for olefinic polymerization according to the present invention is in the time of 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.
Usually, at the described catalyzer for olefinic polymerization, in the alkylaluminium cpd of aluminium and can be as 1-2000 taking the mol ratio of the catalyst component for olefinic polymerization of titanium: 1, be preferably 20-500: 1; The mol ratio of described external donor compound and alkylaluminium cpd can be 0.005-0.5: 1, be preferably 0.01-0.4: 1.
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 conventional various external donor compounds in this area, 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 be 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.
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 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 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 DEG C, is preferably 60-90 DEG C; Polymerization pressure can be normal pressure or pressurization.
The invention will be further described by the following examples.But, 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 catalyzer and application thereof for olefinic polymerization.
(1) preparation of spherical magnesium chloride adducts
In the autoclave of 300L, add the white oil of 90L, silicone oil, the magnesium chloride (94.7mol) of 9.0kg and the ethanol (249.0mol) of 14.5L of 90L, under agitation be warming up to 125 DEG C, and at 125 DEG C, stir 2.5 hours, then, by the mixing liquid obtaining by entering in advance after high-gravity rotating bed in the hexane that is cooled to-30 DEG C, elimination liquid, and with hexane washing five times, obtain the solid matter (being the alcohol adduct of magnesium chloride) of 18kg after dry.
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) that is dissolved in the 45ml in the hexane of 180ml is added wherein, then, be warming up to 60 DEG C, and at this temperature stirring reaction 3h, carry out afterwards press filtration, with hexane washing 5 times, after being dried, obtain spherical magnesium chloride adducts.
Detect the Mg content in this spherical magnesium chloride adducts according to complexometry, detect respectively ethanol in this spherical magnesium chloride adducts and the content of methyl alcohol according to liquid phase chromatographic analysis method, consequently, the mol ratio of magnesium chloride, ethanol and the methyl alcohol in this spherical magnesium chloride adducts is 1: 1.6: 0.6; Adopt Mastersizer 2000 laser particle analyzers (being produced by Malvern Instruments Ltd) to record, the average particulate diameter of the spheroidal particle of magnesium chloride adducts is 42 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 DEG C, the magnesium chloride adducts making in above-mentioned (1) of 40 grams is added wherein, and stir 30min at-20 DEG C.Afterwards, start to be slowly warming up to 110 DEG C, and in temperature-rise period, add the diisobutyl phthalate of 7.5ml, elimination liquid maintain 30min at 110 DEG C after, add again afterwards titanium tetrachloride washing 2 times, finally, with hexane washing 5 times, after being dried, obtain the catalyst component C1 for olefinic polymerization.Adopt grating spectrophotometer, according to the titanium elements content in this catalyst component of spectrophotometry; Detect the magnesium element content in this catalyst component according to complexometry; Detect the diisobutyl phthalate content in this catalyst component according to liquid phase chromatographic analysis method, the mass ratio that result records titanium elements, magnesium elements and diisobutyl phthalate in this catalyst component is 1: 8: 6; Adopt Nikon Eclipse E200 type opticmicroscope-JVC color video camera to observe this catalyst component, 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 hexane solution (concentration of CHMMS is 0.1mmol/ml), the anhydrous hexane of 10ml and the catalyst component C1 for olefinic polymerization of 8mg of the Cyclohexyl Methyl Dimethoxysilane (CHMMS) of hexane solution (concentration of triethyl aluminum is 0.5mmol/ml), the 1ml of the triethyl aluminum of 5ml.Close autoclave, add the hydrogen of 1.5L (standard volume) and the liquid propene of 2.3L, be warming up to 70 DEG C, 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 catalyzer and application thereof for olefinic polymerization.
According to the method for embodiment 1 prepare spherical 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 5.0L.
Comparative example 1
(1) preparation of spherical magnesium chloride adducts
In the autoclave of 300L, add the white oil of 90L, the silicone oil of 90L, magnesium chloride, the ethanol of 14.5L and the Propanal dimethyl acetal of 1.8L (14.7mol) of 9.0kg, under agitation be warming up to 125 DEG C, and at 125 DEG C, stir 2.5 hours, then, by the mixing liquid obtaining by entering in advance after high-gravity rotating bed in the hexane that is cooled to-30 DEG C, elimination liquid, and with hexane washing five times, after being dried, obtain spherical magnesium chloride adducts.
(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, obtains catalyst component DC1.
(3) propylene polymerization
Carry out propylene polymerization according to the method for embodiment 1, difference is, with the catalyst component DC1 replacement catalyst component C1 of identical weight.
Comparative example 2
According to the method for comparative example 1 prepare spherical 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 5.0L.
Embodiment 3
The present embodiment is for illustrating described catalyst component for olefinic polymerization provided by the invention and preparation method thereof and catalyzer and application thereof for olefinic polymerization.
(1) preparation of spherical magnesium chloride adducts
Prepare spherical magnesium chloride adducts according to the method for embodiment 1, difference is, after obtaining magnesium chloride alcohol adduct, in the reactor of 1.6L, add the hexane of 900ml, the magnesium chloride alcohol adduct of 90 grams is added wherein, again the Propanal dimethyl acetal of 10ml is dissolved in the hexane of 180ml, added in reactor, be warming up to 60 DEG C, and reacted 3h at this temperature, carry out afterwards press filtration, with hexane washing 2 times, the solid matter obtaining is added in reactor, and add wherein the hexane of 800ml.Then, by 2 of 8ml, 4-pentanediol dibenzoate is dissolved in the hexane of 100ml, and is added in reactor, is warming up to 60 DEG C, and reacts 2h at this temperature, carries out afterwards press filtration, and with hexane washing 5 times, after being dried, obtains spherical magnesium chloride adducts.
Detect the Mg content in this spherical magnesium chloride adducts according to complexometry, detect respectively ethanol, the methyl alcohol and 2 in this spherical magnesium chloride adducts according to liquid phase chromatographic analysis method, the content of 4-pentanediol dibenzoate, consequently, the mol ratio of magnesium chloride, ethanol, methyl alcohol and 2,4-pentanediol dibenzoate in this spherical magnesium chloride adducts 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 the spheroidal particle of 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, be cooled to-20 DEG C, the spherical adduct of magnesium halides making in above-mentioned (1) of 40 grams is added wherein, and stir 30min at-20 DEG C.Afterwards, start be slowly warming up to 110 DEG C, 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, at 110 DEG C, maintain 30min after elimination liquid.Then, add titanium tetrachloride washing 3 times, finally wash 5 times with hexane, after being dried, obtain the catalyst component C2 for olefinic polymerization.Adopt grating spectrophotometer, according to the titanium elements content in this catalyst component of spectrophotometry; Detect the magnesium element content in this catalyst component according to complexometry; Detect respectively 2 in this catalyst component according to liquid phase chromatographic analysis method, 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
In the autoclave of a 5L, adopt stream of nitrogen gas to purge, then in stream of nitrogen gas, introduce hexane solution (the concentration 0.1mmol/ml of CHMMS), the anhydrous hexane of 10ml and the catalyst component C2 for olefinic polymerization of 4mg of the Cyclohexyl Methyl Dimethoxysilane (CHMMS) of hexane solution (concentration of triethyl aluminum is 0.5mmol/ml), the 0.1ml of the triethyl aluminum of 1ml.Close autoclave, add the hydrogen of 2L (standard volume) and the liquid propene of 2.3L.Be warming up to 70 DEG C, and at this temperature, react 1 hour.
Embodiment 4
The present embodiment is for illustrating described catalyst component for olefinic polymerization provided by the invention and preparation method thereof and catalyzer and application thereof for olefinic polymerization.
According to the method for embodiment 3 prepare spherical 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 3
(1) preparation of spherical 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 at this temperature, stir 2.5 hours, then, by the mixing liquid obtaining by entering in advance after high-gravity rotating bed in the hexane that is cooled to-30 DEG C, elimination liquid, and with hexane washing five times, obtain the solid matter (being the alcohol adduct of magnesium chloride) of 18kg after dry.
(2) for the preparation of the catalyst component of olefinic polymerization
Catalyst component according to the method for embodiment 3 for the preparation of olefinic polymerization, obtains catalyst component DC2.
(3) propylene polymerization
Carry out propylene polymerization according to the method for embodiment 3, difference is, with the catalyst component DC1 replacement catalyst component C1 of identical weight.
Comparative example 4
According to the method for comparative example 3 prepare spherical 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 5
The present embodiment is for illustrating described catalyst component for olefinic polymerization provided by the invention and preparation method thereof and catalyzer and application thereof for olefinic polymerization.
(1) preparation of spherical magnesium chloride adducts
Prepare spherical magnesium chloride adducts according to the method for embodiment 3, difference is, the Propanal dimethyl acetal being dissolved in the hexane of 180ml is 45ml; Replace 2 in the hexane that is dissolved in 100ml with the solution of the salicylic acid ethyl ester that is dissolved in the 7ml in the hexane of 100ml, the solution of 4-pentanediol dibenzoate, thus make magnesium chloride adducts.
Detect the Mg content in this spherical magnesium chloride adducts according to complexometry, detect respectively the content of ethanol, methyl alcohol and salicylic acid ethyl ester in this spherical magnesium chloride adducts according to liquid phase chromatographic analysis method, consequently, the mol ratio of magnesium chloride, ethanol, methyl alcohol and the salicylic acid ethyl ester in this spherical magnesium chloride adducts is 1: 2.1: 0.7: 0.005; Adopt Mastersizer 2000 laser particle analyzers (being produced by Malvern Instruments Ltd) to record, the average particulate diameter of the spheroidal particle of magnesium chloride adducts is 40 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, obtains catalyst component C3.Adopt grating spectrophotometer, according to the titanium elements content in this catalyst component of spectrophotometry; Detect the magnesium element content in this catalyst component according to complexometry; Adopt chromatographic analyzer of liquid phase, detect respectively the diisobutyl phthalate content in this catalyst component according to liquid phase chromatographic analysis method, the mol ratio that result records titanium elements, magnesium elements and diisobutyl phthalate in this catalyst component is 1: 7.5: 5.2.
(3) propylene polymerization
Carry out propylene polymerization according to the method for embodiment 1, difference is, with the catalyst component DC1 replacement catalyst component C1 of identical weight.
Embodiment 6
The present embodiment is for illustrating described catalyst component for olefinic polymerization provided by the invention and preparation method thereof and catalyzer and application thereof for olefinic polymerization.
According to the method for embodiment 5 prepare spherical 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 5.0L.
Test case 1
Adopt Nikon Eclipse E200 type opticmicroscope-JVC color video camera to observe the spherical magnesium chloride adducts of preparation in embodiment 1 and comparative example 1, and the optical microscope photograph of the spherical magnesium chloride adducts of embodiment 1 as shown in Figure 1, the optical microscope photograph of the spherical magnesium chloride adducts of comparative example 1 as shown in Figure 2.
Can be found out by Fig. 1 and Fig. 2, the particle form of the spherical magnesium chloride adducts of embodiment 1 is more regular, is all spherical substantially, and particle size distribution is more concentrated, and there is no that irregular particle exists; And there is a large amount of irregular particles in the spherical magnesium chloride adducts of comparative example 1.
Test case 2
(1) according to the melting index of the method detection polymkeric substance of ASTM D1238-99:
(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, after 6 hours, residuum is dried to constant weight with the extracting of boiling heptane, the polymer weight (g) of gained is degree of isotacticity with 2 ratio;
The result detecting according to aforesaid method is as shown in table 1 below.
Table 1
Can find out that from the data of above-mentioned table 1 catalyst component for olefinic polymerization of prepared in accordance with the method for the present invention has good hydrogen response in propylene polymerization.Concrete, by adopting the melting index of carrying out the polymkeric substance obtaining after propylene polymerization for catalyst component C1, the C2 of olefinic polymerization and C3 to compare and can find out with adopting the melting index of carrying out the polymkeric substance obtaining after propylene polymerization for the catalyst component DC1 of olefinic polymerization and DC2 respectively, with respect to the catalyst component DC1 for olefinic polymerization, there is good hydrogen response for catalyst component C1 and the C3 of olefinic polymerization; With respect to the catalyst component DC2 for olefinic polymerization, there is good hydrogen response for the catalyst component C2 of olefinic polymerization.
Test case 3
The polymkeric substance making in embodiment 3 and comparative example 3 is sieved, and its result is as shown in table 2 below:
Table 2
Data by upper table 2 can be found out, in the process of preparing propene polymer, adopt the fine powder content less (particle size is the fine powder that is generally below 80 orders) of the described propene polymer making for the catalyzer of olefinic polymerization carries out olefinic polyreaction provided by the invention, visible, the described catalyst component for olefinic polymerization provided by the invention is difficult for broken, thereby has good resistance to crumbliness.Particularly, in the time containing polyol ester in described spherical adduct of magnesium halides, this catalyst component that is used for olefinic polymerization has better resistance to crumbliness, thereby the fine powder of resulting polymers still less.
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.
Claims (37)
1. the catalyst component for olefinic polymerization, this catalyst component contains spherical adduct of magnesium halides, titanium compound and internal electron donor compound and reacts the product obtaining, it is characterized in that, described spherical adduct of magnesium halides contains the compound that general formula is MgXY, compound and the methyl alcohol 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.
2. catalyst component according to claim 1, wherein, the general formula of described spherical adduct of magnesium halides is MgXY-mROH-nCH
3oH-qH
2o, wherein, m is 1-2.4, and n is 0.1-1.5, and q is 0-0.8.
3. catalyst component according to claim 2, wherein, in the general formula of described spherical adduct of magnesium halides, m is 1.3-2.2, and n is 0.3-1.2, and q is 0-0.5.
4. according to the catalyst component described in any one in claim 1-3, wherein, the compound that general formula 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.
5. according to the catalyst component described in any one in claim 1-3, wherein, the average particulate diameter of described spherical adduct of magnesium halides is 10-100 micron.
6. catalyst component 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 F, Cl, Br or I, the integer that a is 1-3, the integer that b is 1-4.
7. catalyst component according to claim 6, 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.
8. catalyst component according to claim 1, wherein, described internal electron donor compound is one or more in carboxylicesters, alcohol ester, ether, ketone, amine and silane.
9. catalyst component according to claim 8, wherein, described internal electron donor compound is one or more in monobasic or polyhydric aliphatic family carboxylicesters, monobasic or polynary aromatic carboxylic acid esters, binary alcohol esters and binary ether.
10. catalyst component 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.
11. catalyst components according to claim 10, 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.
12. according to the catalyst component described in any one in claim 1-3, 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; And
(3) make described spherical solid particulate and Propanal dimethyl acetal contact reacts in inert dispersion medium.
13. catalyst components according to claim 12, wherein, in step (1), the temperature of heating is 100-140 DEG C, and the time of heating is 1-5 hour, and 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; With respect to the MgXY in magnesium elements 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.
14. catalyst components according to claim 12, wherein, in step (2), described heat-eliminating medium is inert hydrocarbon solvent; The temperature of described heat-eliminating medium is-30 DEG C to-10 DEG C.
15. catalyst components according to claim 14, 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 DEG C to-10 DEG C.
16. catalyst components according to claim 12, wherein, described catalytic condition in step (3) comprises: temperature of reaction is 40-65 DEG C, reaction times is 1-5 hour, with respect to the MgXY in magnesium elements of 1 mole, the add-on of described Propanal dimethyl acetal is 0.1-1.5 mole.
17. catalyst components according to claim 16, wherein, the described catalytic condition in step (3) comprises: with respect to the MgXY in magnesium elements of 1 mole, the add-on of described Propanal dimethyl acetal is 0.2-1 mole.
18. 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, obtain spherical adduct of magnesium halides; And
(4) described spherical adduct of magnesium halides is reacted with titanium compound, and add internal electron donor compound in one or more time periods in before and after, during the reacting of described spherical adduct of magnesium halides and titanium compound.
19. methods according to claim 18, wherein, in step (1), the temperature of heating is 100-140 DEG C, the time of heating is 1-5 hour.
20. methods according to claim 18, wherein, in step (1), 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.
21. according to the method described in any one in claim 18-20, wherein, in step (1), with respect to the MgXY in magnesium elements 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.
22. according to the method described in any one in claim 18-20, and wherein, the compound that general formula 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.
23. methods 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 DEG C to 0 DEG C.
24. methods according to claim 23, 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 DEG C to-10 DEG C.
25. methods according to claim 18, wherein, the described catalytic condition in step (3) comprises: temperature of reaction is 40-65 DEG C, the reaction times is 1-5 hour; With respect to the MgXY in magnesium elements of 1 mole, the add-on of described Propanal dimethyl acetal is 0.1-1.5 mole.
26. methods according to claim 25, wherein, in step (3), with respect to the MgXY in magnesium elements of 1 mole, the add-on of described Propanal dimethyl acetal is 0.2-1 mole.
27. methods according to claim 18, wherein, in step (4), in the spherical adduct of magnesium halides of magnesium elements, taking the mol ratio of the titanium compound of titanium elements and the add-on of internal electron donor as 1:20-150:0.005-1.
28. methods according to claim 27, wherein, in step (4), in the spherical adduct of magnesium halides of magnesium elements, taking the mol ratio of the titanium compound of titanium elements and the add-on of internal electron donor as 1:30-120:0.01-0.6.
29. methods according to claim 18, 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 F, Cl, Br or I, the integer that a is 1-3, the integer that b is 1-4.
30. methods according to claim 29, 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.
31. methods according to claim 18, wherein, described internal electron donor compound is one or more in carboxylicesters, alcohol ester, ether, ketone, amine and silane.
32. methods according to claim 31, wherein, described internal electron donor compound is one or more in monobasic or polyhydric aliphatic family carboxylicesters, monobasic or polynary aromatic carboxylic acid esters, binary alcohol esters and binary ether.
33. catalyst components for olefinic polymerization of being prepared by the method described in any one in claim 18-32.
The catalyst component for olefinic polymerization in 34. claim 1-17 and 33 described in any one is in the application of the catalyzer for olefinic polymerization.
35. 1 kinds of catalyzer for olefinic polymerization, this catalyzer contains:
(1) catalyst component for olefinic polymerization described in any one in claim 1-17 and 33;
(2) alkylaluminium cpd; And
(3) optional external donor compound.
The catalyzer for olefinic polymerization described in 36. claims 35 is in the application of olefinic polyreaction.
37. 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 35.
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| CN107522799B (en) * | 2016-06-20 | 2020-09-15 | 中国石油化工股份有限公司 | Spherical carrier, olefin polymerization catalyst, preparation method and application thereof, and olefin polymerization method |
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