CN102796208A - 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
- Publication number
- CN102796208A CN102796208A CN2011101420213A CN201110142021A CN102796208A CN 102796208 A CN102796208 A CN 102796208A CN 2011101420213 A CN2011101420213 A CN 2011101420213A CN 201110142021 A CN201110142021 A CN 201110142021A CN 102796208 A CN102796208 A CN 102796208A
- Authority
- CN
- China
- Prior art keywords
- compound
- catalyst component
- magnesium
- titanium
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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 that is used for olefinic polymerization; This is used for the preparation method of the catalyst component of olefinic polymerization; The catalyst component that is used for olefinic polymerization by this method preparation; The said application that is used for the catalyst component of olefinic polymerization at the catalyzer that is used for olefinic polymerization; A kind of catalyzer that is used for olefinic polymerization, this is used for application and the olefine polymerizing process of the catalyzer of olefinic polymerization at olefinic polyreaction.
Background technology
Titanium compound and compound loaded metallocene (Ziegler-Natta) catalyzer that on magnesium halide in active, prepares of electron donor are well known in the prior art.Usually, said magnesium halide in active adopts the adducts of magnesium halide and alcohol, obtains spherical catalyst after it is reacted as carrier and titanium compound and electron donor compound.When this spherical catalyst is used for olefinic polymerization (particularly propylene polymerization), have high polymerization activity and upright structure directional property, resulting polymkeric substance has particle form preferably.
Own disclosed magnesium halide and pure adducts generally include magnesium chloride and pure binary composition.Also comprise a spot of water in some disclosed alcohol adduct.This type of alcohol adduct can be extruded or the preparation of method such as high-speed stirring through spraying drying, spray cooling, high pressure.As: the disclosed magnesium chloride alcohol adduct of US4421674, US4469648, WO8707620, WO9311166, US5100849, US6020279, US4399054, EP0395383, US6127304 and US6323152.When the catalyzer of above-mentioned magnesium chloride alcohol adduct preparation is used for olefinic polymerization, is easy to take place the broken phenomenon of polymkeric substance, thereby causes fine polymer powder more.Its major cause possibly be because in adducts and titanium compound and the electron donor compound reaction process, and the catalyst active center that on the adducts carrier, forms is inhomogeneous to cause.
In order to overcome this shortcoming; People attempt again the electron donor compound is introduced in the preparing carriers of magnesium chloride alcohol adduct in advance; For example: in CN1397568A and CN1563112A technology; Known internal electron donor of the industry such as phthalate compound were introduced in synthesizing of carrier; Form the spherical carrier of " magnesium dichloride-alcohol-phthalic ester " mixture, then this carrier and titanium tetrachloride reaction are formed catalyzer.Disclosed ball type carrier is of a size of D50:70-200, and its catalyzer is used for propylene polymerization, and polymerization activity is lower, is 406gPP/gcat.Disclose a kind of adduct of magnesium halides at CN101050245A, its general formula is MgX
2-mROH-nE-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 are 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; With magnesium halide, alcohol, two-oxyl hydrocarbon compounds and randomly inert media mixing; Under agitation mixture heating up is warmed up to 100-140 ℃; To forming the adduct of magnesium halides melt; Wherein the add-on of magnesium halide is the 0.1-1.0mol/L liquid medium, and the add-on of pure and mild 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 adduct of magnesium halides according to the preparation of the method for this patent application; Like needle-shaped particle, clavate particle, when using this adduct of magnesium halides to be used for olefinic polymerization, can cause resulting polymers also to have a large amount of irregular particles undoubtedly as the catalyzer of carrier.
Summary of the invention
First purpose of the present invention is to overcome to adopt the above-mentioned defective of existing adduct of magnesium halides as the catalyzer that is used for olefinic polymerization of support of the catalyst preparation, and a kind of new catalyst component that is used for olefinic polymerization is provided.
Second purpose of the present invention provides the preparation method that this is used for the catalyst component of olefinic polymerization.
The 3rd purpose of the present invention provides the catalyst component that is used for olefinic polymerization that adopts above-mentioned preparing method's preparation.
The 4th purpose of the present invention provides the said application that is used for the catalyst component of olefinic polymerization at the catalyzer that is used for olefinic polymerization.
The 5th purpose of the present invention provides a kind of catalyzer that is used for olefinic polymerization.
The 6th purpose of the present invention provides the said application that is used for the catalyzer of olefinic polymerization at olefinic polyreaction.
The 7th purpose of the present invention provides a kind of olefine polymerizing process.
The invention provides a kind of catalyst component that is used 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, Said spherical adduct of magnesium halides contains the compound that general formula is MgXY, compound and the methyl alcohol that general formula is ROH; And contain or not moisture, wherein, in formula M gXY; X is a 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 who is used for the catalyst component of olefinic polymerization; This method may further comprise the steps: (1) is that the compound of MgXY and compound that general formula is ROH and optional inert liquid medium mix with general formula; Under agitation with the mixture heating up that obtains to the melt that forms adduct of magnesium halides; Wherein, In formula M gXY; An X is a 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 with said adduct of magnesium halides adds after shearing dissemination in the heat-eliminating medium, forms the spheric solid particulate; (3) make said spheric solid particulate and Propanal dimethyl acetal contact reacts in inert dispersion medium, obtain spherical adduct of magnesium halides; And (4) with the reaction of said spherical adduct of magnesium halides and titanium compound, and before the reaction of said spherical adduct of magnesium halides and titanium compound, during and afterwards in one or more time periods in adding internal electron donor compound.
The present invention also provides the catalyst component that is used for olefinic polymerization by method for preparing.
The present invention also provides the said application that is used for the catalyst component of olefinic polymerization at the catalyzer that is used for olefinic polymerization.
The present invention also provides a kind of catalyzer that is used for olefinic polymerization, and this catalyzer contains: (1) said catalyst component that is used for olefinic polymerization provided by the invention; (2) alkylaluminium cpd; And (3) optional external electron donor compound.
The present invention also provides the said application that is used for the catalyzer of olefinic polymerization at olefinic polyreaction.
The present invention also provides a kind of olefine polymerizing process, and this method comprises: under the olefinic polymerization condition, one or more alkene are contacted with catalyzer, wherein, said catalyzer is the said catalyzer that is used for olefinic polymerization provided by the invention.
Particle form according to the said catalyst component that is used for olefinic polymerization provided by the invention is good; Smooth surface; Good fluidity, and when using the catalyzer that is used for olefinic polymerization comprise this catalyst component that is used for olefinic polymerization to carry out olefinic polymerization, have better hydrogen regulation sensitivity.
Description of drawings
Fig. 1 representes the optical microscope photograph of the spherical adduct of magnesium halides of preparation among the embodiment 1;
Fig. 2 representes the optical microscope photograph of the adduct of magnesium halides of preparation in the Comparative Examples 1;
Fig. 3 representes the catalyst component particulate optical microscope photograph that is used for olefinic polymerization of preparation among the embodiment 1.
Embodiment
According to a first aspect of the invention; The invention provides a kind of catalyst component that is used 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 are obtained; Wherein, said spherical adduct of magnesium halides contains the compound that general formula is MgXY, compound and the methyl alcohol that general formula is ROH, and contains or not moisture; Wherein, In formula M gXY, X is a 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 said spherical adduct of magnesium halides can be expressed as MgXY-mROH-nCH
3OH-qH
2O, wherein, in MgXY, X is a 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 said spherical adduct of magnesium halides, general formula is that the compound of MgXY refers to magnesium halide.In the preferred case, in formula M gXY, X is a halogen, and Y is C
1-C
6Alkyl, C
1-C
6Alkoxyl group, C
6-C
12Aryl or C
6-C
12Aryloxy.Said halogen is preferably chlorine or bromine.Said C
1-C
6Alkyl for example can be methyl, ethyl, propyl group, sec.-propyl, butyl or isobutyl-, said C
1-C
6Alkoxyl group for example can be methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy or isobutoxy, said C
6-C
12Aryl for example can be for phenyl, o-tolyl, a tolyl, p-methylphenyl, adjacent ethylbenzene base, an ethylbenzene base, to the second phenyl or naphthyl, said C
6-C
12Aryloxy for example can be phenoxy group or naphthyloxy.
Under further preferable case, general formula is that the compound of MgXY is one or more in magnesium dichloride, dibrominated magnesium, phenoxy group magnesium chloride, isopropoxy magnesium chloride and the butoxy magnesium chloride.
In said spherical adduct of magnesium halides, general formula is that the compound of ROH refers to the alcohol except that 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.Said C
2-C
8Alkyl for example can be ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl, hexyl, isohexyl, heptyl, different heptyl, octyl group or iso-octyl.Said C
3-C
8Cycloalkyl for example can be cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.Said C
6-C
10Aryl for example can be for phenyl, o-tolyl, a tolyl, p-methylphenyl, adjacent ethylbenzene base, an ethylbenzene base, to the second phenyl or naphthyl.
Under further preferable case, 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 the 2-Ethylhexyl Alcohol.
According to one embodiment of the present invention, said spherical adduct of magnesium halides can also contain or not contain o-hydroxybenzoate and/or polyol ester.In this case, said spherical adduct of magnesium halides can be by formula M gXY-mROH-nCH
3OH-sG-tDOE-qH
2O representes that wherein, MgXY, ROH, m, n and q are all identical with above-mentioned definition, and G representes o-hydroxybenzoate, and s is 0-0.05, and DOE representes polyol ester, and t is 0-0.1.When s and t are 0 (being not contain o-hydroxybenzoate and polyol ester in the said 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 s is not when being 0 (be to contain o-hydroxybenzoate in the said spherical adduct of magnesium halides, but do not contain 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 t is not when being 0 (be to contain polyol ester in the said spherical adduct of magnesium halides, but do not contain o-hydroxybenzoate), formula M gXY-mROH-nCH
3OH-sG-tDOE-qH
2O is equal to formula M gXY-mROH-nCH
3OH-tDOE-qH
2O; When s and t all were not 0, said spherical adduct of magnesium halides contained o-hydroxybenzoate and polyol ester.
In the preferred case, said spherical adduct of magnesium halides also contains o-hydroxybenzoate and/or polyol ester.In this preferred implementation; The particle form of said spherical adduct of magnesium halides is good; Make the catalyzer that is used for olefinic polymerization that comprises this sphere adduct of magnesium halides have particle form preferably, and this catalyzer have anti-preferably crumbliness in olefinic polyreaction.
Contain under the situation of o-hydroxybenzoate at said spherical adduct of magnesium halides, the general formula of said 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 representes said 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.
Said o-hydroxybenzoate can be represented by following formula (1):
Wherein, R
1Be C
1-C
12Straight or branched alkyl, C
3-C
10Cycloalkyl, C
6-C
10Aryl or C
7-C
10Aralkyl.Said C
1-C
12The straight or branched alkyl for example can be methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, isopentyl, hexyl or isohexyl, said C
3-C
10Cycloalkyl for example can be cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, said C
6-C
10Aryl for example can be for phenyl, o-tolyl, a tolyl, p-methylphenyl, adjacent ethylbenzene base, an ethylbenzene base, to the second phenyl or naphthyl, said C
7-C
10Aralkyl for example can be indenyl, benzyl or phenylethyl.Under further preferable case, said 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 the isobutyl o-hydroxybenzoate.
Contain under the situation of polyol ester at said spherical adduct of magnesium halides, the general formula of said 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 representes said 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.
Said 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 the 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, i.e. total k carbon atom and R in the 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, said heteroatoms can be in halogen, nitrogen, oxygen, sulphur, silicon and the phosphorus one or more, k is the integer of 0-10, when k=0, then substituting group is R in the polyol ester shown in the formula (2)
4, R
5Carbon atom directly and substituting group be R
6, R
7The carbon atom key connect.
In the preferred case, said polyol ester is a binary alcohol esters, and said binary alcohol esters can be represented by following formula (3):
Wherein, R
2And R
3Identical with the definition in the 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, said heteroatoms can be in halogen, nitrogen, oxygen, sulphur, silicon and the phosphorus one or more.
In the present invention, said binary alcohol esters for example can be 1, the ammediol dibenzoate; The 2-methyl isophthalic acid; The ammediol dibenzoate; 2-ethyl-1, the ammediol dibenzoate; 2,2-dimethyl-1; The ammediol dibenzoate; (R)-and 1-phenyl-1, the ammediol dibenzoate; 1,3-phenylbenzene-1; The ammediol dibenzoate; 1; 3-phenylbenzene-1, ammediol two n Propanoic acid esters; 1,3-phenylbenzene-2-methyl isophthalic acid; The ammediol dipropionate; 1; 3-phenylbenzene-2-methyl isophthalic acid, the ammediol diacetate esters; 1,3-phenylbenzene-2; 2-dimethyl-1; The ammediol dibenzoate; 1,3-phenylbenzene-2,2-dimethyl-1; The ammediol dipropionate; 1; 3-di-t-butyl-2-ethyl-1, the ammediol dibenzoate; 1,3-phenylbenzene-1; The ammediol diacetate esters; 1; 3-di-isopropyl-1,3-propyl alcohol two (4-butylbenzoic acid) ester; 1-phenyl-2-amino-1, the ammediol 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; The 2-methyl isophthalic acid; 3-pentanediol two (Chlorodracylic acid) ester; The 2-methyl isophthalic acid; 3-pentanediol two (p-methylbenzoic acid) ester; 2-butyl-1,3-pentanediol two (p-methylbenzoic acid) ester; The 2-methyl isophthalic acid, 3-pentanediol two (p-tert-butyl benzoic acid) ester; The 2-methyl isophthalic acid; 3-pentanediol pivalate; The 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; The 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, two pairs of fluoro methyl benzoic acid esters of 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-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; 9; 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-(benzoyloxy methyl)-9-(the third carboxyl methyl) fluorenes; 9; Two (the third carboxyl methyl) fluorenes of 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 part binary alcohol esters can be commercially available, and other can be synthetic with reference to the method described in the CN1436796A.
In preferred implementation of the present invention, the average particulate diameter of said spherical adduct of magnesium halides can be 10-100 μ m, is preferably 20-80 μ m.In this preferred implementation, the catalyzer that is used for olefinic polymerization that comprises this sphere adduct of magnesium halides has good anti-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 said catalyst component that is used 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; The condition of the reaction of said spherical adduct of magnesium halides, titanium compound and internal electron donor compound does not have special qualification; Under the preferable case, the condition of this reaction can comprise: temperature of reaction is 80-130 ℃, and the reaction times is 0.5-10 hour.
In the present invention, said titanium compound can be used for the conventional various titanium compounds that use of process of the catalyzer of olefinic polymerization for preparation.Usually, said titanium compound can be Ti (OR ') for general formula for example
3-aZ
aAnd/or Ti (OR ')
4-bZ
bCompound, wherein, R ' is C
1-C
20Alkyl, Z is F, Cl, Br or I, a is the integer of 1-3, b is the integer of 1-4.Under the preferable case, said 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 the titanous chloride.
In the present invention; Said internal electron donor compound can be used for the conventional various internal electron donor compounds that use of process of the catalyzer of olefinic polymerization for preparation; For example can be in carboxylicesters, alcohol ester, ether, ketone, amine and the silane one or more, be preferably in monobasic or polyhydric aliphatic family carboxylicesters, monobasic or polynary aromatic carboxylic acid esters, binary alcohol esters and the binary ether one or more.
Said monobasic or polyhydric aliphatic carboxylicesters for example can be 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-methylsuccinic acid diisobutyl ester; 2-ethyl-2-methylsuccinic acid diethyl ester; Diethylene adipate; Polycizer W 260; Ethyl sebacate; Uniflex DBS; Diethyl maleate; Maleic acid n-butyl; In naphthalene dicarboxylic acids diethyl ester and the naphthalene dicarboxylic acids dibutylester one or more.
Said monobasic or polynary aromatic carboxylic acid esters for example can be 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 one or more.
Said binary alcohol esters can be the compound by following formula (4) expression,
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 the 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, i.e. total d carbon atom and R in the 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, said heteroatoms can be in halogen, nitrogen, oxygen, sulphur, silicon and the phosphorus one or more, d is the integer of 0-10, when d=0, then substituting group is R in the binary alcohol esters shown in the formula (4)
10, R
11Carbon atom directly and substituting group be R
12, R
13The carbon atom key connect.
Under the preferable case, said binary alcohol esters is the compound by following formula (5) expression:
Wherein, R
14And R
15Identical with the definition in the 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, said heteroatoms can be in halogen, nitrogen, oxygen, sulphur, silicon and the phosphorus one or more.
In the present invention, said binary alcohol esters for example can be 1, the ammediol dibenzoate; The 2-methyl isophthalic acid; The ammediol dibenzoate; 2-ethyl-1, the ammediol dibenzoate; 2,2-dimethyl-1; The ammediol dibenzoate; (R)-and 1-phenyl-1, the ammediol dibenzoate; 1,3-phenylbenzene-1; The ammediol dibenzoate; 1; 3-phenylbenzene-1, ammediol two n Propanoic acid esters; 1,3-phenylbenzene-2-methyl isophthalic acid; The ammediol dipropionate; 1; 3-phenylbenzene-2-methyl isophthalic acid, the ammediol diacetate esters; 1,3-phenylbenzene-2; 2-dimethyl-1; The ammediol dibenzoate; 1,3-phenylbenzene-2,2-dimethyl-1; The ammediol dipropionate; 1; 3-di-t-butyl-2-ethyl-1, the ammediol dibenzoate; 1,3-phenylbenzene-1; The ammediol diacetate esters; 1; 3-di-isopropyl-1,3-propyl alcohol two (4-butylbenzoic acid) ester; 1-phenyl-2-amino-1, the ammediol 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; The 2-methyl isophthalic acid; 3-pentanediol two (Chlorodracylic acid) ester; The 2-methyl isophthalic acid; 3-pentanediol two (p-methylbenzoic acid) ester; 2-butyl-1,3-pentanediol two (p-methylbenzoic acid) ester; The 2-methyl isophthalic acid, 3-pentanediol two (p-tert-butyl benzoic acid) ester; The 2-methyl isophthalic acid; 3-pentanediol pivalate; The 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; The 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, two pairs of fluoro methyl benzoic acid esters of 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; 9; 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-(benzoyloxy methyl)-9-(the third carboxyl methyl) fluorenes; 9; Two (the third carboxyl methyl) fluorenes of 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 part binary alcohol esters can be commercially available, and other can be synthetic with reference to the method described in the CN1436796A.
Said binary ether can be the compound by following formula (6) expression,
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 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
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 mutual bonding forms.
In the present invention; Said binary ether for example can be 2-(2-ethylhexyl)-1; The 3-Propanal dimethyl acetal; 2-sec.-propyl-1; The 3-Propanal dimethyl acetal; 2-butyl-1; The 3-Propanal dimethyl acetal; 2-sec-butyl-1; The 3-Propanal dimethyl acetal; 2-cyclohexyl-1; The 3-Propanal dimethyl acetal; 2-phenyl-1; The 3-Propanal dimethyl acetal; 2-(2-phenylethyl)-1; The 3-Propanal dimethyl acetal; 2-(2-cyclohexyl ethyl)-1; The 3-Propanal dimethyl acetal; 2-(right-chloro-phenyl-)-1; The 3-Propanal dimethyl acetal; 2-(diphenyl methyl)-1; The 3-Propanal dimethyl acetal; 2; 2-dicyclohexyl-1; The 3-Propanal dimethyl acetal; 2; 2-two cyclopentyl-1; The 3-Propanal dimethyl acetal; 2; 2-diethyl-1; The 3-Propanal dimethyl acetal; 2; 2-dipropyl-1; The 3-Propanal dimethyl acetal; 2; 2-di-isopropyl-1; The 3-Propanal dimethyl acetal; 2; 2-dibutyl-1; The 3-Propanal dimethyl acetal; 2-methyl-2-propyl group-1; The 3-Propanal dimethyl acetal; 2-methyl-2-benzyl-1; The 3-Propanal dimethyl acetal; 2-methyl-2-ethyl-1; The 3-Propanal dimethyl acetal; 2-methyl-2-sec.-propyl-1; The 3-Propanal dimethyl acetal; 2-methyl-2-phenyl-1; The 3-Propanal dimethyl acetal; 2-methyl-2-cyclohexyl-1; The 3-Propanal dimethyl acetal; 2; Two (the 2-cyclohexyl ethyls)-1 of 2-; The 3-Propanal dimethyl acetal; 2-methyl-2-isobutyl--1; The 3-Propanal dimethyl acetal; 2-methyl-2-(2-ethylhexyl)-1; The 3-Propanal dimethyl acetal; 2; 2-diisobutyl-1; The 3-Propanal dimethyl acetal; 2; 2-phenylbenzene-1; The 3-Propanal dimethyl acetal; 2; 2-dibenzyl-1; The 3-Propanal dimethyl acetal; 2; Two (cyclohexyl methyl)-1 of 2-; The 3-Propanal dimethyl acetal; 2-isobutyl--2-sec.-propyl-1; The 3-Propanal dimethyl acetal; 2-(1-methyl butyl)-2-sec.-propyl-1; The 3-Propanal dimethyl acetal; 2-sec.-propyl-2-isopentyl-1; The 3-Propanal dimethyl acetal; 2-phenyl-2-sec.-propyl-1; The 3-Propanal dimethyl acetal; 2-phenyl-2-the second month in a season-butyl-1; The 3-Propanal dimethyl acetal; 2-benzyl-2-sec.-propyl-1; The 3-Propanal dimethyl acetal; 2-cyclopentyl-2-sec.-propyl-1; The 3-Propanal dimethyl acetal; 2-cyclopentyl-2-the second month in a season-butyl-1; The 3-Propanal dimethyl acetal; 2-cyclohexyl-2-sec.-propyl-1; The 3-Propanal dimethyl acetal; 2-cyclohexyl-2-the second month in a season-butyl-1; The 3-Propanal dimethyl acetal; 2-sec.-propyl-2-the second month in a season-butyl-1; The 3-Propanal dimethyl acetal; 2-cyclohexyl-2-cyclohexyl methyl-1; 3-Propanal dimethyl acetal and 9, one or more in the 9-dimethoxy-methyl fluorenes.
According to the said catalyst component that is used for olefinic polymerization provided by the invention, the preparation method of said spherical adduct of magnesium halides can may further comprise the steps:
(1) be that the compound of MgXY and compound that general formula is ROH and optional inert liquid medium mix with general formula, under agitation with the mixture heating up that obtains to the melt that forms adduct of magnesium halides;
(2) melt with said adduct of magnesium halides adds after shearing dissemination in the heat-eliminating medium, forms the spheric solid particulate; And
(3) make said spheric solid particulate and Propanal dimethyl acetal contact reacts in inert dispersion medium;
Wherein, said general formula be compound and the general formula of MgXY be ROH compound all with preamble describe identical.
In the preparation process of said spherical adduct of magnesium halides; In above-mentioned steps (1), general formula is that the add-on of the compound of MgXY and the compound that general formula is ROH can suitably be selected according to the proportioning of each component in the spherical adduct of magnesium halides that goes for.Under the preferable case, general formula is that the mol ratio of the add-on of the compound of MgXY and the compound that general formula is ROH is 1: 1-8 is preferably 1: 2-6.Said general formula be compound and the general formula of MgXY be compound and the preamble of ROH describe identical.
In the preparation process of said spherical adduct of magnesium halides, in above-mentioned steps (1), the purpose of said heating is in order to make magnesium halide, pure and mild inert liquid medium form magnesium halide and pure adducts melt.The condition of said heating does not have concrete qualification, can confirm according to the concrete halogenated magnesium compound that uses.Said heating condition can comprise usually: Heating temperature is more than 80 ℃, and be more than 1 hour heat-up time.Under the preferable case, said heating condition comprises: Heating temperature is 100-140 ℃, and be 1-5 hour heat-up time.
In the preparation process of said spherical adduct of magnesium halides; Chemically interactive liquid medium can variously not take place with spherical adduct of magnesium halides as what this area was used always in the inert liquid medium that uses in the step (1), for example: silicoorganic compound and/or aliphatic hydrocarbon based compound.Particularly, said inert liquid medium can be 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, Yellow Protopet 2A, vaseline oil and the white oil one or more.Under the further preferred situation, said inert liquid medium is white oil and silicone oil.The consumption of said inert liquid medium does not have special qualification, the common MgXY in magnesium elements (being the magnesium halide that adds in the step (1)) with respect to 1 mole, and the consumption of said inert liquid medium is 0.8-10L.
In the preparation process of said spherical adduct of magnesium halides; In above-mentioned steps (2); Said 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); The disclosed mixture with adduct of magnesium halides and inert liquid medium of CN1267508C is rotated (speed of rotation can be 1000-3000 rev/min) in the hypergravity bed disperses; The disclosed mixture with adduct of magnesium halides and silicone oil and white oil of CN1463990A is exported with 1500-8000 rev/min speed with mulser; The disclosed emulsifying mixture that will contain adduct of magnesium halides through spray method of US6020279.
In the preparation process of said spherical adduct of magnesium halides; In above-mentioned steps (2), it is the melt supercooled formation spheric solid particulate for the adduct of magnesium halides after will disperseing that the melt of said adduct of magnesium halides is added after shearing dissemination in the heat-eliminating medium.In the present invention, said heat-eliminating medium is preferably inert hydrocarbon solvent, and more preferably lower boiling inert hydrocarbon solvent for example can be in pentane, hexane, heptane, the gasoline or petrol ether one or more.The temperature of said heat-eliminating medium can be-40 ℃ to 0 ℃, is preferably-30 ℃ to-10 ℃.
In the preparation process of said spherical adduct of magnesium halides; After said chilling and make before solid particulate and the Propanal dimethyl acetal contact reacts, the preparation method of said spherical adduct of magnesium halides comprises also that preferably the solid particulate that obtains after to said chilling with inert organic solvents washs 1-10 time.Said inert organic solvents for example can be in pentane, hexane, heptane, the gasoline or petrol ether one or more.
In the preparation process of said spherical adduct of magnesium halides, the said catalytic condition in the step (3) does not have special qualification, and under the preferable case, said 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 elements with respect to 1 mole (being the magnesium halide that adds in the step (1)), the add-on of the Propanal dimethyl acetal in the step (3) is the 0.1-1.5 mole, more preferably the 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 said spherical adduct of magnesium halides, in step (3), what said inert dispersion medium for example can be in pentane, hexane and the heptane is at least a.
In the preferred case, the preparation method of said spherical adduct of magnesium halides comprises that also the spheroidal particle of the adduct of magnesium halides that will pass through the said process acquisition contacts with o-hydroxybenzoate and/or polyol ester mixing.
Spheroidal particle with said adduct of magnesium halides further mixes under the situation about contacting with o-hydroxybenzoate, and the add-on of said o-hydroxybenzoate and the mol ratio of MgXY can be 0.002-0.5, are preferably 0.02-0.2; The spheroidal particle of said adduct of magnesium halides mixes the condition that contacts with o-hydroxybenzoate and can comprise: temperature is 40-65 ℃, and the time is 1-5 hour.Said o-hydroxybenzoate is preferably the compound shown in the above-mentioned formula (1).
Spheroidal particle with said adduct of magnesium halides further mixes under the situation about contacting with polyol ester, and the add-on of said 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; The spheroidal particle of said adduct of magnesium halides mixes the condition that contacts with polyol ester and can comprise: temperature is 40-65 ℃, and the time is 1-5 hour.Said polyol ester is preferably the polyol ester shown in the above-mentioned formula (2), further is preferably the binary alcohol esters shown in the above-mentioned formula (3).
According to a second aspect of the invention, the present invention also provides a kind of preparation method who is used for the catalyst component of olefinic polymerization, and this method may further comprise the steps:
(1) be that the compound of MgXY and compound that general formula is ROH and optional inert liquid medium mix with general formula; Under agitation with the mixture heating up that obtains to the melt that forms adduct of magnesium halides, wherein, in formula M gXY; An X is a 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 with said adduct of magnesium halides adds after shearing dissemination in the heat-eliminating medium, forms the spheric solid particulate;
(3) make said spheric solid particulate and Propanal dimethyl acetal contact reacts in inert dispersion medium, obtain spherical adduct of magnesium halides; And
(4) with the reaction of said spherical adduct of magnesium halides and titanium compound, and before the reaction of said spherical adduct of magnesium halides and titanium compound, during and afterwards in one or more time periods in adding internal electron donor compound.
In the above-mentioned preparation method who is used for the catalyst component of olefinic polymerization, the step (1) among the preparation method of the spherical adduct of magnesium halides that step (1) to (3) and preamble are described is identical to (3), does not do at this and gives unnecessary details.
In the said preparation method who is used for the catalytic component of olefinic polymerization; The said spherical adduct of magnesium halides of step (4) can adopt the mode identical with prior art to carry out with the titanium compound reaction; Concrete; For example; In step (4); The concrete operation method of said spherical adduct of magnesium halides and titanium compound reaction is preferably included: titanium compound is cooled to below 0 ℃ (is preferably-5 to-25 ℃); Add the spherical adduct of magnesium halides that obtains in the step (3) then; And under this temperature, mixed 10-60 minute; Be warming up to reaction temperature (promptly about 80-130 ℃) afterwards, and under this reaction temperature, kept 0.5-10 hour.In the said preparation method who is used for the catalyst component of olefinic polymerization; Said internal electron donor compound before the reaction of said spherical adduct of magnesium halides and titanium compound, during and afterwards in one or more time periods in add, preferably before the reaction of said spherical adduct of magnesium halides and titanium compound, add.Time period before the reaction of said spherical adduct of magnesium halides and titanium compound is meant after said spherical adduct of magnesium halides adds in the reactor and the time period before being warming up to temperature of reaction.
In the said preparation method who is used for the catalyst component of olefinic polymerization; In step (4); In the spherical adduct of magnesium halides of magnesium elements, can be 1 in the mol ratio of the add-on of the titanium compound of titanium elements and internal electron donor: 20-150: 0.005-1 is preferably 1: 30-120: 0.01-0.6.
In the said preparation method who is used for the catalyst component of olefinic polymerization, said titanium compound and internal electron donor respectively with preamble in titanium compound and the internal electron donor described identical.
In a kind of preferred implementation; The said preparation method who is used for the catalyst component of olefinic polymerization also is included in before the spherical adduct of magnesium halides and titanium compound contact reacts that step (3) is obtained; It is mixed with o-hydroxybenzoate and/or polyol ester contact, with the further particle form that improves adduct of magnesium halides.
Said spherical adduct of magnesium halides is being mixed under the situation about contacting with o-hydroxybenzoate, and the add-on of said o-hydroxybenzoate and the mol ratio of MgXY can be 0.002-0.5, are preferably 0.02-0.2; The spheroidal particle of said adduct of magnesium halides mixes the condition that contacts with o-hydroxybenzoate and can comprise: temperature is 40-65 ℃, and the time is 1-5 hour.The o-hydroxybenzoate of describing in said o-hydroxybenzoate and the preamble is identical.
The spheroidal particle of said adduct of magnesium halides and polyol ester are being mixed under the situation about contacting, and the add-on of said 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; The spheroidal particle of said adduct of magnesium halides mixes the condition that contacts with polyol ester and can comprise: temperature is 40-65 ℃, and the time is 1-5 hour.The polyol ester of describing in said polyol ester and the preamble is identical.
According to a third aspect of the present invention, the present invention also provides the catalyst component that is used for olefinic polymerization by method for preparing.
According to a fourth aspect of the present invention, the present invention also provides the said application that is used for the catalyst component of olefinic polymerization at the catalyzer that is used for olefinic polymerization.
According to a fifth aspect of the present invention, the present invention also provides a kind of catalyzer that is used for olefinic polymerization, and this catalyzer contains:
(1) the said catalyst component that is used for olefinic polymerization provided by the invention;
(2) alkylaluminium cpd; And
(3) Ren Xuan external electron donor compound.
Said composition and the preparation method who is used for the catalyst component of olefinic polymerization carried out detailed description at preamble, repeats no more at this.
The catalyzer that is used for olefinic polymerization according to the present invention has used the catalyst component that is used for olefinic polymerization according to the present invention; Therefore the catalyzer that is used for olefinic polymerization according to the present invention is when being used as the catalyzer of olefinic polyreaction; Not only demonstrate high polymerization activity; And have excellent hydrogen response and high stereotaxis ability, and can prepare the good polymkeric substance of particle shape.Therefore, the catalyzer that is used for olefinic polymerization according to the present invention all limits less than special for the kind and the consumption of alkylaluminium cpd and external electron donor compound.
Usually,, can be 1-2000 in the alkylaluminium cpd of aluminium with in the mol ratio of the catalyst component that is used for olefinic polymerization of titanium at the said catalyzer that is used for olefinic polymerization: 1, be preferably 20-500: 1; The mol ratio of said external electron donor compound and alkylaluminium cpd can be 0.005-0.5: 1, be preferably 0.01-0.4: 1.
Said alkylaluminium cpd can be this area various alkylaluminium cpds commonly used.For example, said alkylaluminium cpd can be 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 the dichloro one n-hexyl aluminium one or more.
Said external electron donor compound can be the various external electron donor compounds that this area is commonly used, and for example, said external electron donor can be in carboxylic acid, acid anhydrides, ester, ketone, ether, alcohol, organo phosphorous compounds and the silicoorganic compound one or more; Preferably, said external electron donor is silicoorganic compound.The instance of said silicoorganic compound can for but be not limited to: cyclohexyl methyl dimethoxy silane, 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; 1-three fluoro-2-propyl group)-2-ethyl piperidine base dimethoxy silane and (1; 1,1-three fluoro-2-propyl group)-methyl dimethoxysilane.
According to a sixth aspect of the invention, the present invention also provides the said application that is used for the catalyzer of 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 this method comprises: under the olefinic polymerization condition, one or more alkene are contacted with catalyzer; Wherein, said catalyzer is the catalyzer that is used for olefinic polymerization according to the present invention.
Olefine polymerizing process according to the present invention can prepare the good polymkeric substance of particle form through using the catalyzer that is used for olefinic polymerization according to the present invention.Said olefine polymerizing process of the present invention is for olefinic polymerization condition and the not special qualification of employed alkene.
Said alkene for example can be 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 the vinylbenzene one or more, is preferably in ethene, propylene, 1-butylene, 2-butylene and the vinylbenzene one or more.
According to olefine polymerizing process of the present invention, said olefinic polymerization can be carried out according to the ordinary method of this area.For example, said olefinic polymerization can be mass polymerization, vapour phase polymerization or slurry polymerization.According to olefine polymerizing process of the present invention, said 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.
Below through embodiment the present invention is described further.Yet, should be understood that these embodiment only are used for explanation and explain the present invention, are not limited to the present invention.
Embodiment 1
Present embodiment is used to said catalyst component that is used for olefinic polymerization provided by the invention and preparation method thereof is described and the catalyzer and the application thereof that are used for olefinic polymerization.
(1) preparation of spherical magnesium chloride adducts
In the autoclave of 300L; The white oil, the silicone oil of 90L, the magnesium chloride (94.7mol) of 9.0kg and the ethanol (249.0mol) of 14.5L that add 90L; Under agitation be warming up to 125 ℃; And under 125 ℃, stirred 2.5 hours; Then, the mixing liquid that obtains is got in the hexane that is cooled to-30 ℃ in advance elimination liquid through high-gravity rotating bed back; And, obtain the solid matter (being the alcohol adduct of magnesium chloride) of 18kg after the drying with hexane wash five times.
In the reaction kettle of 1.6L; The hexane that adds 900ml; The solid matter of the above-mentioned preparation of 90 grams is added wherein; The Propanal dimethyl acetal solution (content of Propanal dimethyl acetal is 0.37mol) that will be dissolved in the 45ml in the hexane of 180ml again adds wherein, then, is warming up to 60 ℃; And under this temperature stirring reaction 3h; Carry out press filtration afterwards,, obtain spherical magnesium chloride adducts after the drying with hexane wash 5 times.
Detect the Mg content in this sphere magnesium chloride adducts according to complexometry; Detect ethanol and the content of methyl alcohol in this sphere magnesium chloride adducts respectively according to liquid phase chromatographic analysis method; Consequently, the mol ratio of magnesium chloride, ethanol and the methyl alcohol in this sphere 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) be used 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 that makes in above-mentioned (1) with 40 grams adds wherein, and stirs 30min down at-20 ℃.Afterwards; Beginning slowly is warming up to 110 ℃; And in temperature-rise period, add the diisobutyl phthalate of 7.5ml; Elimination liquid after keeping 30min under 110 ℃; Add titanium tetrachloride washing 2 times afterwards again; Use hexane wash at last 5 times, obtain being used for the catalyst component C1 of olefinic polymerization after the drying.Adopt grating spectrophotometer, detect the titanium elements content in this catalyst component according to 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 the 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 that this catalyst component is observed, 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 hexane solution (concentration of CHMMS is 0.1mmol/ml), the anhydrous hexane of 10ml and the catalyst component C1 that is used for olefinic polymerization of 8mg of the cyclohexyl methyl dimethoxy silane (CHMMS) of the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of the triethyl aluminum of introducing 5ml, 1ml in stream of nitrogen gas.Close autoclave, add the hydrogen of 1.5L (standard volume) and the liquid propene of 2.3L, be warming up to 70 ℃, and under this temperature, reacted 1 hour.
Embodiment 2
Present embodiment is used to said catalyst component that is used for olefinic polymerization provided by the invention and preparation method thereof is described and the catalyzer and the application thereof that are used for olefinic polymerization.
Method according to embodiment 1 prepares spherical magnesium chloride adducts, preparation is used for the catalyst component of olefinic polymerization and carries out propylene polymerization, and different is that the add-on of hydrogen is 5.0L in the propylene polymerization process.
Comparative Examples 1
(1) preparation of spherical magnesium chloride adducts
In the autoclave of 300L; The white oil, the silicone oil of 90L, the magnesium chloride of 9.0kg, the ethanol of 14.5L and the Propanal dimethyl acetal (14.7mol) of 1.8L that add 90L; Under agitation be warming up to 125 ℃; And under 125 ℃, stirred 2.5 hours; Then, the mixing liquid that obtains is got in the hexane that is cooled to-30 ℃ in advance elimination liquid through high-gravity rotating bed back; And, obtain spherical magnesium chloride adducts after the drying with hexane wash five times.
(2) be used for the preparation of the catalyst component of olefinic polymerization
Method according to embodiment 1 prepares the catalyst component that is used for olefinic polymerization, obtains catalyst component DC1.
(3) propylene polymerization
Method according to embodiment 1 is carried out propylene polymerization, and different is, replaces catalyst component C1 with the catalyst component DC1 of identical weight.
Comparative Examples 2
Method according to Comparative Examples 1 prepares spherical magnesium chloride adducts, preparation is used for the catalyst component of olefinic polymerization and carries out propylene polymerization, and different is that the add-on of hydrogen is 5.0L in the propylene polymerization process.
Embodiment 3
Present embodiment is used to said catalyst component that is used for olefinic polymerization provided by the invention and preparation method thereof is described and the catalyzer and the application thereof that are used for olefinic polymerization.
(1) preparation of spherical magnesium chloride adducts
Method according to embodiment 1 prepares spherical magnesium chloride adducts; Different is; After obtaining the magnesium chloride alcohol adduct; In the reaction kettle of 1.6L; The hexane that adds 900ml; The magnesium chloride alcohol adduct of 90 grams is added wherein; Propanal dimethyl acetal with 10ml is dissolved in the hexane of 180ml again; It is added in the reaction kettle, be warming up to 60 ℃, and under this temperature, react 3h; Carry out press filtration afterwards; With hexane wash 2 times, the solid matter that obtains is added in the reaction kettle, and to the hexane that wherein adds 800ml.Then, with 2 of 8ml, 4-pentanediol dibenzoate is dissolved in the hexane of 100ml, and it is added in reaction kettle, is warming up to 60 ℃, and under this temperature, reacts 2h, carries out press filtration afterwards, and with hexane wash 5 times, obtains spherical magnesium chloride adducts after the drying.
Detect the Mg content in this sphere magnesium chloride adducts according to complexometry; Detect ethanol, methyl alcohol and 2 in this sphere magnesium chloride adducts respectively according to liquid phase chromatographic analysis method; The content of 4-pentanediol dibenzoate; Consequently; Magnesium chloride, ethanol, methyl alcohol and 2 in this sphere magnesium chloride adducts, the mol ratio of 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 the spheroidal particle of magnesium chloride adducts is 43 microns.
(2) be used 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 ℃, the spherical adduct of magnesium halides that makes in above-mentioned (1) with 40 grams adds wherein, and stirs 30min down at-20 ℃.Afterwards, beginning slowly is warming up to 110 ℃, in temperature-rise period, adds 2 of 6.5ml, 2-sec.-propyl-2-isopentyl-1 of 4-pentanediol dibenzoate and 6.5ml, 3-Propanal dimethyl acetal, elimination liquid after keeping 30min under 110 ℃.Then, add titanium tetrachloride washing 3 times, wash 5 times with hexane at last, obtain being used for the catalyst component C2 of olefinic polymerization after the drying.Adopt grating spectrophotometer, detect the titanium elements content in this catalyst component according to spectrophotometry; Detect the magnesium element content in this catalyst component according to complexometry; Detect 2 in this catalyst component respectively according to liquid phase chromatographic analysis method; 4-pentanediol dibenzoate and 2-sec.-propyl-2-isopentyl-1; 3-Propanal dimethyl acetal content; The 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 hexane solution (the concentration 0.1mmol/ml of CHMMS), the anhydrous hexane of 10ml and the catalyst component C2 that is used for olefinic polymerization of 4mg of the cyclohexyl methyl dimethoxy silane (CHMMS) of the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of the triethyl aluminum of introducing 1ml, 0.1ml in stream of nitrogen gas.Close autoclave, add the hydrogen of 2L (standard volume) and the liquid propene of 2.3L.Be warming up to 70 ℃, and under this temperature, reacted 1 hour.
Embodiment 4
Present embodiment is used to said catalyst component that is used for olefinic polymerization provided by the invention and preparation method thereof is described and the catalyzer and the application thereof that are used for olefinic polymerization.
Method according to embodiment 3 prepares spherical magnesium chloride adducts, preparation is used for the catalyst component of olefinic polymerization and carries out propylene polymerization, and different is that the add-on of hydrogen is 6.5L in the propylene polymerization process.
Comparative Examples 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 ℃; And under this temperature, stirred 2.5 hours; Then, the mixing liquid that obtains is got in the hexane that is cooled to-30 ℃ in advance elimination liquid through high-gravity rotating bed back; And, obtain the solid matter (being the alcohol adduct of magnesium chloride) of 18kg after the drying with hexane wash five times.
(2) be used for the preparation of the catalyst component of olefinic polymerization
Method according to embodiment 3 prepares the catalyst component that is used for olefinic polymerization, obtains catalyst component DC2.
(3) propylene polymerization
Method according to embodiment 3 is carried out propylene polymerization, and different is, replaces catalyst component C1 with the catalyst component DC1 of identical weight.
Comparative Examples 4
Method according to Comparative Examples 3 prepares spherical magnesium chloride adducts, preparation is used for the catalyst component of olefinic polymerization and carries out propylene polymerization, and different is that the add-on of hydrogen is 6.5L in the propylene polymerization process.
Embodiment 5
Present embodiment is used to said catalyst component that is used for olefinic polymerization provided by the invention and preparation method thereof is described and the catalyzer and the application thereof that are used for olefinic polymerization.
(1) preparation of spherical magnesium chloride adducts
Method according to embodiment 3 prepares spherical magnesium chloride adducts, and different is, the Propanal dimethyl acetal that is dissolved in the hexane of 180ml is 45ml; Replace being dissolved in 2 in the hexane of 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 the magnesium chloride adducts.
Detect the Mg content in this sphere magnesium chloride adducts according to complexometry; Detect the content of ethanol, methyl alcohol and salicylic acid ethyl ester in this sphere magnesium chloride adducts respectively 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 sphere 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) be used for the preparation of the catalyst component of olefinic polymerization
Method according to embodiment 1 prepares the catalyst component that is used for olefinic polymerization, obtains catalyst component C3.Adopt grating spectrophotometer, detect the titanium elements content in this catalyst component according to spectrophotometry; Detect the magnesium element content in this catalyst component according to complexometry; Adopt chromatographic analyzer of liquid phase; Detect the diisobutyl phthalate content in this catalyst component respectively according to liquid phase chromatographic analysis method, the mol ratio that the result records titanium elements, magnesium elements and diisobutyl phthalate in this catalyst component is 1: 7.5: 5.2.
(3) propylene polymerization
Method according to embodiment 1 is carried out propylene polymerization, and different is, replaces catalyst component C1 with the catalyst component DC1 of identical weight.
Embodiment 6
Present embodiment is used to said catalyst component that is used for olefinic polymerization provided by the invention and preparation method thereof is described and the catalyzer and the application thereof that are used for olefinic polymerization.
Method according to embodiment 5 prepares spherical magnesium chloride adducts, preparation is used for the catalyst component of olefinic polymerization and carries out propylene polymerization, and different is that the add-on of hydrogen is 5.0L in the propylene polymerization process.
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 the Comparative Examples 1; And the optical microscope photograph of the spherical magnesium chloride adducts of embodiment 1 as shown in Figure 1, and the optical microscope photograph of the spherical magnesium chloride adducts of Comparative Examples 1 as shown in Figure 2.
Can be found out that by Fig. 1 and Fig. 2 the particle form of the spherical magnesium chloride adducts of embodiment 1 is more regular, all be spheric basically, and particle size distribution is more concentrated, and do not have irregular particle to exist basically; And have a large amount of irregular particles in the spherical magnesium chloride adducts of Comparative Examples 1.
Test case 2
(1) detect the melting index of polymkeric substance according to the method for ASTM D1238-99:
(2) adopt the heptane extraction process to detect the polymkeric substance degree of isotacticity; This method comprises: 2 gram exsiccant polymer samples are placed in the extractor; After 6 hours, residuum is dried to constant weight with boiling heptane extracting, the polymer weight of gained (g) is degree of isotacticity with 2 ratio;
Result according to aforesaid method detects is as shown in table 1 below.
Table 1
Can find out that from the data of above-mentioned table 1 catalyst component that is used for olefinic polymerization of prepared in accordance with the method for the present invention has better hydrogen regulation sensitivity in propylene polymerization.Concrete; The melting index of the polymkeric substance that catalyst component DC1 and the DC2 that the melting index of the polymkeric substance that carries out through catalyst component C1, C2 and the C3 that employing is used for olefinic polymerization obtaining behind the propylene polymerization is used for olefinic polymerization with employing respectively carries out obtaining behind the propylene polymerization compares and can find out; With respect to the catalyst component DC1 that is used for olefinic polymerization, the catalyst component C1 and the C3 that are used for olefinic polymerization have better hydrogen regulation sensitivity; With respect to the catalyst component DC2 that is used for olefinic polymerization, the catalyst component C2 that is used for olefinic polymerization has better hydrogen regulation sensitivity.
Test case 3
The polymkeric substance that makes in embodiment 3 and the Comparative Examples 3 is sieved, and its result is as shown in table 2 below:
Table 2
Data by last table 2 can be found out; In the process of preparation propene polymer; The fine powder content of the propene polymer that adopts the said catalyzer that is used for olefinic polymerization provided by the invention to carry out olefinic polyreaction and make less (particle size is the fine powder that is generally below 80 orders); It is thus clear that; The said catalyst component that is used for olefinic polymerization provided by the invention is difficult for broken, thereby has anti-preferably crumbliness.Particularly, when containing polyol ester in the said spherical adduct of magnesium halides, this catalyst component that is used for olefinic polymerization has better anti-crumbliness, thereby the fine powder of resulting polymers still less.
Above embodiment only is used to describe preferred implementation of the present invention; But; The present invention is not limited to the detail in the above-mentioned embodiment; In technical conceive scope 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 (27)
1. catalyst component that is used 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; It is characterized in that; Said spherical adduct of magnesium halides contains the compound that general formula is MgXY, compound and the methyl alcohol that general formula is ROH; And contain or not moisture, wherein, in formula M gXY; X is a 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 said 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; Preferably, m is 1.3-2.2, and n is 0.3-1.2, and q is 0-0.5.
3. catalyst component according to claim 1, wherein, general formula is that the compound of MgXY is one or more in magnesium dichloride, dibrominated magnesium, phenoxy group magnesium chloride, isopropoxy magnesium chloride and the 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 the 2-Ethylhexyl Alcohol.
4. catalyst component according to claim 1, wherein, the average particulate diameter of said spherical adduct of magnesium halides is the 10-100 micron.
5. catalyst component according to claim 1, wherein, said 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, a is the integer of 1-3, b is the integer of 1-4; Said titanium compound is preferably 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 the titanous chloride.
6. catalyst component according to claim 1; Wherein, Said internal electron donor compound is one or more in carboxylicesters, alcohol ester, ether, ketone, amine and the silane, is preferably in monobasic or polyhydric aliphatic family carboxylicesters, monobasic or polynary aromatic carboxylic acid esters, binary alcohol esters and the binary ether one or more.
7. catalyst component according to claim 1, wherein, at the said catalyst component that is used for olefinic polymerization, the weight ratio of titanium elements, magnesium elements and internal electron donor compound is 1: 5-15: 2-15 is preferably 1: 6-13: 3-12.
8. according to any described catalyst component among the claim 1-7, wherein, the preparation method of said spherical adduct of magnesium halides may further comprise the steps:
(1) be that the compound of MgXY and compound that general formula is ROH and optional inert liquid medium mix with general formula, under agitation with the mixture heating up that obtains to the melt that forms adduct of magnesium halides, wherein, in formula M gXY, X is a halogen, 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 with said adduct of magnesium halides adds after shearing dissemination in the heat-eliminating medium, forms the spheric solid particulate; And
(3) make said spheric solid particulate and Propanal dimethyl acetal contact reacts in inert dispersion medium.
9. catalyst component according to claim 8, wherein, in step (1), the temperature of heating is 100-140 ℃, and the time of heating is 1-5 hour, and general formula is that the mol ratio of the add-on of the compound of MgXY and the compound that general formula is ROH is 1: 1-8; With respect to 1 mole the MgXY in magnesium elements, the consumption of said inert liquid medium is 0.8-10L, and said inert liquid medium is silicoorganic compound and/or aliphatic hydrocarbon based compound.
10. catalyst component according to claim 8, wherein, in step (2), said heat-eliminating medium is an inert hydrocarbon solvent, is preferably in pentane, hexane, heptane, the gasoline or petrol ether one or more; The temperature of said heat-eliminating medium is-40 ℃ to 0 ℃, is preferably-30 ℃ to-10 ℃.
11. catalyst component according to claim 8; Wherein, Said catalytic condition in the step (3) comprises: temperature of reaction is 40-65 ℃; Reaction times is 1-5 hour; MgXY with respect to 1 mole in magnesium elements; The add-on of said Propanal dimethyl acetal is the 0.1-1.5 mole, is preferably the 0.2-1 mole.
12. a preparation method who is used for the catalyst component of olefinic polymerization, this method may further comprise the steps:
(1) be that the compound of MgXY and compound that general formula is ROH and optional inert liquid medium mix with general formula; Under agitation with the mixture heating up that obtains to the melt that forms adduct of magnesium halides, wherein, in formula M gXY; An X is a 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 with said adduct of magnesium halides adds after shearing dissemination in the heat-eliminating medium, forms the spheric solid particulate;
(3) make said spheric solid particulate and Propanal dimethyl acetal contact reacts in inert dispersion medium, obtain spherical adduct of magnesium halides; And
(4) with the reaction of said spherical adduct of magnesium halides and titanium compound, and before the reaction of said spherical adduct of magnesium halides and titanium compound, during and afterwards in one or more time periods in adding internal electron donor compound.
13. method according to claim 12, wherein, in step (1), the temperature of heating is 100-140 ℃, and the time of heating is 1-5 hour.
14. according to claim 12 or 13 described methods, wherein, in step (1), general formula is that the mol ratio of the add-on of the compound of MgXY and the compound that general formula is ROH is 1: 1-8.
15. according to claim 12 or 13 described methods; Wherein, in step (1), with respect to 1 mole MgXY in magnesium elements; The consumption of said inert liquid medium is 0.8-10L, and said inert liquid medium is silicoorganic compound and/or aliphatic hydrocarbon based compound.
16. method according to claim 12, wherein, general formula is that the compound of MgXY is one or more in magnesium dichloride, dibrominated magnesium, phenoxy group magnesium chloride, isopropoxy magnesium chloride and the 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 the 2-Ethylhexyl Alcohol.
17. method according to claim 12, wherein, in step (2), said heat-eliminating medium is an inert hydrocarbon solvent, is preferably in pentane, hexane, heptane, the gasoline or petrol ether one or more; The temperature of said heat-eliminating medium is-40 ℃ to 0 ℃, is preferably-30 ℃ to-10 ℃.
18. method according to claim 12, wherein, the said catalytic condition in the step (3) comprises: temperature of reaction is 40-65 ℃, and the reaction times is 1-5 hour.
19. according to claim 12 or 18 described methods, wherein, in step (3), with respect to 1 mole the MgXY in magnesium elements, the add-on of said Propanal dimethyl acetal is the 0.1-1.5 mole, is preferably the 0.2-1 mole.
20. method according to claim 12; Wherein, In step (4), be 1 in the spherical adduct of magnesium halides of magnesium elements, in the mol ratio of the add-on of the titanium compound of titanium elements and internal electron donor: 20-150: 0.005-1 is preferably 1: 30-120: 0.01-0.6.
21. method according to claim 12, wherein, said 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, a is the integer of 1-3, b is the integer of 1-4; Be preferably 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 the titanous chloride one or more.
22. method according to claim 12; Wherein, Said internal electron donor compound is one or more in carboxylicesters, alcohol ester, ether, ketone, amine and the silane, is preferably in monobasic or polyhydric aliphatic family carboxylicesters, monobasic or polynary aromatic carboxylic acid esters, binary alcohol esters and the binary ether one or more.
23. the catalyst component that is used for olefinic polymerization by any described method preparation among the claim 12-22.
24. any described application that is used for the catalyst component of olefinic polymerization at the catalyzer that is used for olefinic polymerization in claim 1-11 and 23.
25. a catalyzer that is used for olefinic polymerization, this catalyzer contains:
(1) any described catalyst component that is used for olefinic polymerization among the claim 1-11 and 23;
(2) alkylaluminium cpd; And
(3) Ren Xuan external electron donor compound.
26. the described application that is used for the catalyzer of olefinic polymerization at olefinic polyreaction of claim 25.
27. an olefine polymerizing process, this method comprises: under the olefinic polymerization condition, one or more alkene are contacted with catalyzer, it is characterized in that, said catalyzer is the catalyzer that is used for olefinic polymerization described in the claim 25.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110142021.3A CN102796208B (en) | 2011-05-27 | 2011-05-27 | Catalyst component for olefin polymerization and preparation method thereof, catalyst for olefin polymerization, and olefin polymerization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110142021.3A CN102796208B (en) | 2011-05-27 | 2011-05-27 | Catalyst component for olefin polymerization and preparation method thereof, catalyst for olefin polymerization, and olefin polymerization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102796208A true CN102796208A (en) | 2012-11-28 |
| CN102796208B CN102796208B (en) | 2014-08-06 |
Family
ID=47195536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110142021.3A Active CN102796208B (en) | 2011-05-27 | 2011-05-27 | Catalyst component for olefin polymerization and preparation method thereof, catalyst for olefin polymerization, and olefin polymerization method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102796208B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804112A (en) * | 2014-01-24 | 2015-07-29 | 大唐国际化工技术研究院有限公司 | Primary catalyst, preparation method and application thereof and catalyst composition containing the same |
| CN104558271B (en) * | 2013-10-09 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of carrier for olefin polymerization catalyst and preparation method thereof |
| CN104558272B (en) * | 2013-10-09 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of carrier for olefin polymerization catalyst and preparation method thereof |
| CN106608941A (en) * | 2017-02-22 | 2017-05-03 | 营口市风光化工有限公司 | Carrier used for olefin polymerization catalyst and preparation method thereof |
| CN106832069A (en) * | 2017-02-22 | 2017-06-13 | 营口市风光化工有限公司 | A kind of catalyst for olefinic polymerization and preparation method thereof |
| CN107522799A (en) * | 2016-06-20 | 2017-12-29 | 中国石油化工股份有限公司 | Ball type carrier and olefin polymerization catalysis and its preparation method and application and the method for olefinic polymerization |
| CN107840905A (en) * | 2016-09-21 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of ingredient of solid catalyst, catalyst system and pre-polymerized catalyst for olefinic polymerization |
| US11261198B2 (en) | 2016-06-20 | 2022-03-01 | Shionogi & Co., Ltd. | Process for preparing substituted polycyclic pyridone derivative and crystal thereof |
| CN116041593A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Preparation method of spherical magnesium halide adduct and product and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4399054A (en) * | 1978-08-22 | 1983-08-16 | Montedison S.P.A. | Catalyst components and catalysts for the polymerization of alpha-olefins |
| CN1072690A (en) * | 1991-11-25 | 1993-06-02 | 埃尼凯姆·埃拉斯托麦里 | The method of the elastocopolymer of preparation ethene |
| CN1875038A (en) * | 2003-11-04 | 2006-12-06 | 德古萨股份公司 | Spherical particles |
| CN101050245A (en) * | 2006-04-06 | 2007-10-10 | 中国石油化工股份有限公司 | Adduct of magnesium halides, preparation method, and application |
| CN101955556A (en) * | 2010-09-10 | 2011-01-26 | 北京化工大学 | Preparation method and application of spherical magnesium halide carrier |
-
2011
- 2011-05-27 CN CN201110142021.3A patent/CN102796208B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4399054A (en) * | 1978-08-22 | 1983-08-16 | Montedison S.P.A. | Catalyst components and catalysts for the polymerization of alpha-olefins |
| CN1072690A (en) * | 1991-11-25 | 1993-06-02 | 埃尼凯姆·埃拉斯托麦里 | The method of the elastocopolymer of preparation ethene |
| CN1875038A (en) * | 2003-11-04 | 2006-12-06 | 德古萨股份公司 | Spherical particles |
| CN101050245A (en) * | 2006-04-06 | 2007-10-10 | 中国石油化工股份有限公司 | Adduct of magnesium halides, preparation method, and application |
| CN101955556A (en) * | 2010-09-10 | 2011-01-26 | 北京化工大学 | Preparation method and application of spherical magnesium halide carrier |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558271B (en) * | 2013-10-09 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of carrier for olefin polymerization catalyst and preparation method thereof |
| CN104558272B (en) * | 2013-10-09 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of carrier for olefin polymerization catalyst and preparation method thereof |
| CN104804112A (en) * | 2014-01-24 | 2015-07-29 | 大唐国际化工技术研究院有限公司 | Primary catalyst, preparation method and application thereof and catalyst composition containing the same |
| CN104804112B (en) * | 2014-01-24 | 2017-11-17 | 大唐国际化工技术研究院有限公司 | A kind of major catalyst, its preparation method, using and containing its carbon monoxide-olefin polymeric |
| US11807648B2 (en) | 2016-06-20 | 2023-11-07 | Shionogi & Co., Ltd. | Process for preparing substituted polycyclic pyridone derivative and crystal thereof |
| CN107522799A (en) * | 2016-06-20 | 2017-12-29 | 中国石油化工股份有限公司 | Ball type carrier and olefin polymerization catalysis and its preparation method and application and the method for olefinic polymerization |
| US11261198B2 (en) | 2016-06-20 | 2022-03-01 | Shionogi & Co., Ltd. | Process for preparing substituted polycyclic pyridone derivative and crystal thereof |
| 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 |
| CN107840905B (en) * | 2016-09-21 | 2020-04-07 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization, catalyst system and prepolymerization catalyst |
| CN107840905A (en) * | 2016-09-21 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of ingredient of solid catalyst, catalyst system and pre-polymerized catalyst for olefinic polymerization |
| CN106608941A (en) * | 2017-02-22 | 2017-05-03 | 营口市风光化工有限公司 | Carrier used for olefin polymerization catalyst and preparation method thereof |
| CN106608941B (en) * | 2017-02-22 | 2019-03-29 | 营口风光新材料股份有限公司 | A kind of carrier and preparation method thereof for olefin polymerization catalysis |
| CN106832069B (en) * | 2017-02-22 | 2019-03-08 | 营口风光新材料股份有限公司 | A kind of catalyst and preparation method thereof for olefinic polymerization |
| CN106832069A (en) * | 2017-02-22 | 2017-06-13 | 营口市风光化工有限公司 | A kind of catalyst for olefinic polymerization and preparation method thereof |
| CN116041593A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Preparation method of spherical magnesium halide adduct and product and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102796208B (en) | 2014-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102796208B (en) | Catalyst component for olefin polymerization and preparation method thereof, catalyst for olefin polymerization, and olefin polymerization method | |
| CN102137876B (en) | Catalyst component for olefin polymerization and catalyst comprising the same | |
| CN101486776B (en) | Catalyst component for olefinic polymerization , and catalyst thereof | |
| CN102453128B (en) | Catalyst component for olefin polymerization and catalyst thereof | |
| CN102040680B (en) | Catalyst component and catalyst for olefin polymerization | |
| CN101165074B (en) | Catalyst component used for olefin polymerization and catalyst thereof | |
| CN101724102B (en) | Catalyst component for olefin polymerization and catalyst thereof | |
| CN102796210B (en) | Catalyst component and catalyst system for olefin polymerization, application of catalyst component and catalyst system, and olefin polymerization method | |
| CN101724101B (en) | Catalyzer component for olefin polymerization and catalyzer thereof | |
| KR20120039016A (en) | Spherical magnesium halide adduct, catalyst component and catalyst for olefin polymerization prepared therefrom | |
| CN102796212B (en) | Catalyst component and catalyst system for olefin polymerization, applications thereof and olefin polymerization method | |
| CN102796209B (en) | Catalyst component for olefin polymerization, method for preparing catalyst component, catalyst for olefin polymerization and method for olefin polymerization | |
| GB2530212A (en) | Catalyst component for use in olefin polymerization reaction, catalyst, and application | |
| CN103788239B (en) | A kind of catalyst solid component of olefin polymerization and olefin polymerization catalysis and application thereof | |
| CN103788248A (en) | Catalyst component used for olefin polymerization, applications thereof, catalyst used for olefin polymerization, applications of the catalyst and olefin polymerization method | |
| CN104558273B (en) | Catalytic component for olefinic polymerization and preparation method thereof and for the catalyst of olefinic polymerization and olefine polymerizing process | |
| CN102796211B (en) | Catalyst component for olefin polymerization and preparation method thereof, catalyst for olefin polymerization, and olefin polymerization method | |
| CN102796128B (en) | A kind of Spherical magnesium halide adduct and its preparation method and application | |
| TWI473827B (en) | Magnesium halide adducts, catalyst components including them and catalysts, and the above-mentioned production methods and applications | |
| CN103788241A (en) | Olefin polymerization catalyst solid component and processing method thereof, and olefin polymerization catalyst and application thereof | |
| CN103788247A (en) | Catalyst component used for olefin polymerization, applications thereof, catalyst used for olefin polymerization, applications of the catalyst and olefin polymerization method | |
| CN104558274B (en) | A kind of solids containing titanium catalytic component for olefinic polyreaction | |
| CN102796132B (en) | Spherical magnesium halide adduct and preparation method and application thereof | |
| CN102796213A (en) | Catalyst component and catalyst system for olefin polymerization, applications thereof and olefin polymerization method | |
| CN103788242B (en) | Catalyst solid component of olefin polymerization and preparation method thereof and olefin polymerization catalysis and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |