CN105566532A - Catalyst component for olefin polymerization, preparation method thereof and catalyst adopting catalyst component - Google Patents
Catalyst component for olefin polymerization, preparation method thereof and catalyst adopting catalyst component Download PDFInfo
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- CN105566532A CN105566532A CN201410554333.9A CN201410554333A CN105566532A CN 105566532 A CN105566532 A CN 105566532A CN 201410554333 A CN201410554333 A CN 201410554333A CN 105566532 A CN105566532 A CN 105566532A
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- biphenyl dicarboxylic
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Abstract
The invention discloses a catalyst component for olefin polymerization. The catalyst component comprises titanium, halogen, magnesium and an internal electron donor compound as shown in the formula I; in the formula I, R1 and R2 are separately selected from substituted or unsubstituted C1-C20 hydrocarbyl groups; R3-R10 can be same or different and are separately selected from hydrogen and substituted or unsubstituted C1-C20 hydrocarbyl groups; R3-R10 can be optionally connected to form a ring or not. According to the invention, a novel internal electronic donor system is adopted to obtain the catalyst with excellent comprehensive property. When the catalyst is used for olefin polymerization, the catalyst is better in polymerization activity, and the obtained polymer is high in stacking density, high in isotacticity, wide in molecular weight distribution and high in melting index.
Description
Technical field
The present invention relates to a kind of catalyst component containing ad hoc structure electron donor compound and preparation method thereof.The invention still further relates to the catalyzer containing described catalyst component and application in olefin polymerization thereof.
Background technology
Using magnesium, titanium, halogen and electron donor as the catalyzer that the solid titanium catalyst component of basal component is formed, namely Ziegler-Natta catalyst known in the field, can be used for CH
2=CHR olefinic polyreaction.Particularly when its for there is 3 carbon or more carbon atom alpha-olefine polymerizing in time, the polymkeric substance of higher yields and higher tacticity can be obtained.As everyone knows, internal electron donor compound is one of requisite composition in Ziegler-Natta catalyst component.From early stage disclosed monocarboxylic acid ester compound, such as ethyl benzoate, the binary aromatic carboxylic acid's ester compound widely used up till now, such as n-butyl phthalate or o-benzoic acid diisobutyl ester, arrive recent disclosed 1 again, 3-bis-ethers (CN1020448C), succinate compound (CN1313869) and 1,3-diol-lipid (CN1213080C) compound, the development of internal electron donor compound result in polyolefin catalyst and constantly updates just.
The catalyzer that phthalate compound is prepared as internal electron donor is for having high activity and degree of isotacticity during olefinic polymerization, but recent research finds, phthalate compound to reproductive system and liver all toxic, European Union, the countries in the world such as the U.S. have been put into effect ban to this compounds and have been limited its use.
Along with the research of polyolefine technology is goed deep into, people wish to develop the internal electron donor compound made new advances, and to obtain the catalyzer of high comprehensive performance, thus adapt to the needs of olefinic polymerization development.
Summary of the invention
For deficiency of the prior art, contriver, by deep research and experiment repeatedly, provides a kind of catalyst component for olefinic polymerization (or claim ingredient of solid catalyst) and comprises the catalyzer of described catalyst component.Can prepare high reactivity, high hydrogen tonality according to catalyst solid constituent provided by the invention, the catalyzer of good stereotaxis ability, and be polymerized the polyolefin molecular weight wider distribution obtained, the catalyzer containing this component is particularly suitable for CH
2the polymerization of=CHR alkene, wherein, R is hydrogen or C
1-C
6alkyl or aryl, especially propylene polymerization.
According to an aspect of the present invention, provide a kind of catalyst component for olefin, comprise the internal electron donor compound shown in titanium, halogen, magnesium and formula I,
In formula, R
1and R
2can be identical or not identical, be selected from substituted or unsubstituted C independently of one another
1-C
20alkyl, be preferably selected from substituted or unsubstituted C
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl and C
7-C
20aralkyl; R
3-R
10can be identical or not identical, be selected from hydrogen and substituted or unsubstituted C independently of one another
1-C
20alkyl, be preferably selected from hydrogen and substituted or unsubstituted C
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
7-C
20alkaryl; R
3-R
10optionally connect into ring or not Cheng Huan.
Catalyst according to the invention component (or claiming ingredient of solid catalyst, catalyst solid constituent), the C of described replacement
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
7-C
20the group that alkaryl etc. replaces, refer to that the atom in described group is substituted, as as described in alkyl, cycloalkyl, hydrogen atom on aryl or alkaryl etc. optionally replaced by halogen (mixing) atom, alkyl or alkoxyl group, the carbon atom on described main chain is optionally by hybrid atom MCM-41.As described R
3-R
10when connecting into ring, described ring contains double bond or heteroatoms.
According in a specific embodiment of catalyst component of the present invention, described R
1and R
2be selected from substituted or unsubstituted C
1-C
10alkyl, C
3-C
10cycloalkyl, C
6-C
10aryl, C
7-C
10aralkyl and C
7-C
10alkaryl; Described R
3-R
10be selected from hydrogen and substituted or unsubstituted C
1-C
10alkyl, C
3-C
10cycloalkyl and C
6-C
10aryl.
According in a preferred embodiment of catalyst component of the present invention, described R
1and R
2be selected from substituted or unsubstituted C
1-C
8alkyl, phenyl, C
7-C
10alkyl phenyl and C
7-C
10alkoxyl phenyl; As methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, phenyl, aminomethyl phenyl and p-methoxy-phenyl etc.; Described R
3-R
10be selected from hydrogen and substituted or unsubstituted C
1-C
6alkyl.
According to the catalyst component in the present invention, for the internal electron donor compound shown in described formula (I), suitable compound includes but not limited to: 2,2 '-biphenyl dicarboxylic acid dimethyl ester, 2,2 '-biphenyl dicarboxylic acid diethyl ester, 2,2 '-biphenyl dicarboxylic acid di-n-propyl ester, 2,2 '-biphenyl dicarboxylic acid diisopropyl ester, 2,2 '-biphenyl dicarboxylic acid di-n-butyl, 2,2 '-biphenyl dicarboxylic acid diisobutyl ester, 2,2 '-biphenyl dicarboxylic acid two (1-methyl) propyl ester, 2,2 '-biphenyl dicarboxylic acid di tert butyl carbonate, 2,2 '-biphenyl dicarboxylic acid two n-pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (1-methyl) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (2-methyl) butyl ester, 2,2 '-biphenyl dicarboxylic acid diisoamyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 '-dimethyl) propyl ester, 2, the special pentyl ester of 2 '-biphenyl dicarboxylic acid two, 2,2 '-biphenyl dicarboxylic acid two (1,2-dimethyl) propyl ester, 2, the just own ester of 2 '-biphenyl dicarboxylic acid, 2,2 '-biphenyl dicarboxylic acid two (1-methyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (2-methyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (3-methyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two dissident ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 '-dimethyl) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,2 '-dimethyl) butyl ester, 2, the special own ester of 2 '-biphenyl dicarboxylic acid two, 2,2 '-biphenyl dicarboxylic acid two (1,2-dimethyl) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,3-dimethyl) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,3-dimethyl) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 2-trimethylammonium) propyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,2,2 '-trimethylammonium) propyl ester, 2, the positive heptyl ester of 2 '-biphenyl dicarboxylic acid, 2,2 '-biphenyl dicarboxylic acid two (1-methyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (2-methyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (3-methyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (4-methyl) own ester, 2,2 '-biphenyl dicarboxylic acid two isocyanate, 2,2 '-biphenyl dicarboxylic acid two (1,1 '-dimethyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,2 '-dimethyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (3,3 '-dimethyl) pentyl ester, 2, the special heptyl ester of 2 '-biphenyl dicarboxylic acid two, 2,2 '-biphenyl dicarboxylic acid two (1,2-dimethyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,3-dimethyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (Isosorbide-5-Nitrae-dimethyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,3-dimethyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,4-dimethyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (3,4-dimethyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 2-trimethylammonium) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 3-trimethylammonium) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,2,2 '-trimethylammonium) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,2 ', 3-trimethylammonium) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,3,3 '-trimethylammonium) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,3,3 '-trimethylammonium) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 2,2 '-tetramethyl-) propyl ester, 2,2 '-biphenyl dicarboxylic acid n-octyl, 2,2 '-biphenyl dicarboxylic acid two (1-methyl) heptyl ester, 2,2 '-biphenyl dicarboxylic acid two (2-methyl) heptyl ester, 2,2 '-biphenyl dicarboxylic acid two (3-methyl) heptyl ester, 2,2 '-biphenyl dicarboxylic acid two (4-methyl) heptyl ester, 2,2 '-biphenyl dicarboxylic acid two (5-methyl) heptyl ester, 2,2 '-biphenyl dicarboxylic acid di-isooctyl, 2,2 '-biphenyl dicarboxylic acid two (1,1 '-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (2,2 '-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (3,3 '-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (4,4 '-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (5,5 '-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (1,2-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (1,3-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (Isosorbide-5-Nitrae-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (1,5-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (2,3-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (2,4-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (2,5-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (3,4-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (3,5-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (4,5-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 2-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 3-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 4-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,2,2 '-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,2 ', 3-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,2 ', 4-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,3,3 '-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,3,3 '-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (3,3 ', 4-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (Isosorbide-5-Nitrae, 4 '-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,4,4 '-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (3,4,4 '-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 2,2 '-tetramethyl-) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 3,3 '-tetramethyl-) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,2 ', 3,3 '-tetramethyl-) butyl ester, 2,2 '-diphenyl bibenzoate, 2,2 '-biphenyl dicarboxylic acid two (adjacent methyl) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (to methyl) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (methyl) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (O-methoxy) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (to methoxyl group) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (meta-methoxy) phenyl ester, be preferably selected from 2,2 '-biphenyl dicarboxylic acid dimethyl ester, 2,2 '-biphenyl dicarboxylic acid diethyl ester, 2,2 '-biphenyl dicarboxylic acid di-n-propyl ester, 2,2 '-biphenyl dicarboxylic acid diisopropyl ester, 2,2 '-biphenyl dicarboxylic acid di-n-butyl, 2,2 '-biphenyl dicarboxylic acid diisobutyl ester, 2,2 '-biphenyl dicarboxylic acid di tert butyl carbonate, 2,2 '-biphenyl dicarboxylic acid two n-pentyl ester, 2,2 '-biphenyl dicarboxylic acid diisoamyl ester, 2, the just own ester of 2 '-biphenyl dicarboxylic acid, 2,2 '-biphenyl dicarboxylic acid two dissident ester, 2, the positive heptyl ester of 2 '-biphenyl dicarboxylic acid, 2,2 '-biphenyl dicarboxylic acid isocyanate, 2,2 '-biphenyl dicarboxylic acid n-octyl, 2, the different monooctyl ester of 2 '-biphenyl dicarboxylic acid, 2,2 '-diphenyl bibenzoate, 2,2 '-biphenyl dicarboxylic acid two (adjacent methyl) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (to methyl) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (methyl) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (O-methoxy) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (to methoxyl group) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (meta-methoxy) phenyl ester, more preferably 2 are selected from, 2 '-biphenyl dicarboxylic acid dimethyl ester, 2, 2 '-biphenyl dicarboxylic acid diethyl ester, 2, 2 '-biphenyl dicarboxylic acid di-n-propyl ester, 2, 2 '-biphenyl dicarboxylic acid diisopropyl ester, 2, 2 '-biphenyl dicarboxylic acid di-n-butyl, 2, 2 '-biphenyl dicarboxylic acid diisobutyl ester, 2, 2 '-biphenyl dicarboxylic acid di tert butyl carbonate, 2, 2 '-biphenyl dicarboxylic acid two n-pentyl ester, 2, 2 '-biphenyl dicarboxylic acid diisoamyl ester, 2, the just own ester of 2 '-biphenyl dicarboxylic acid, 2, 2 '-biphenyl dicarboxylic acid dissident ester, 2, 2 '-diphenyl bibenzoate, 2, 2 '-biphenyl dicarboxylic acid two (adjacent methyl) phenyl ester, 2, 2 '-biphenyl dicarboxylic acid two (to methyl) phenyl ester, 2, 2 '-biphenyl dicarboxylic acid two (O-methoxy) phenyl ester, 2, 2 '-biphenyl dicarboxylic acid two (to methoxyl group) phenyl ester.
According to catalyst component of the present invention, the content of described titanium (element) is 1.0-8.0wt%, is preferably 1.6-6.0wt%; The content of magnesium (element) is 10-70wt%, is preferably 15-40wt%; The content of halogen (element) is 20-90wt%, is preferably 30-85%; Internal electron donor compound content shown in formula I is 2-30wt%, is preferably 3-20wt%.
According to a specific embodiment of catalyst component of the present invention, it comprises the internal electron donor shown in magnesium compound, titanium compound and general formula I is carried out catalytic product in a solvent.Consumption for internal electron donor compound shown in the titanium compound of described catalyst component, magnesium compound and formula I is not particularly limited, and can be respectively conventional substances and the consumption of this area.
In a preferred embodiment, described magnesium compound is selected from formula M gR
4r
5shown magnesium compound, formula M gR
4r
5pH
2the hydrate of the magnesium compound shown in O and formula M gR
4r
5qR
6the alcohol adducts of the magnesium compound shown in OH, in general formula, R
4and R
5be selected from halogen, C independently of one another
1-C
8the alkoxyl group of straight or branched and C
1-C
8straight or branched alkyl; P and q is separately selected from 0.1-6, preferred 2-3.5; R
6for C
1-C
18alkyl, be preferably C
1-C
8alkyl, be more preferably selected from methyl, ethyl, n-propyl and sec.-propyl.Such as, described magnesium compound can be dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two pentyloxy magnesium, two oxygen base magnesium, two (2-ethyl) oxygen base magnesium, methoxyl group magnesium chloride, methoxyl group magnesium bromide, methoxyl group magnesium iodide, oxyethyl group magnesium chloride, oxyethyl group magnesium bromide, oxyethyl group magnesium iodide, propoxy-magnesium chloride, propoxy-magnesium bromide, propoxy-magnesium iodide, butoxy magnesium chloride, butoxy magnesium bromide, butoxy magnesium iodide, methylmagnesium-chloride, ethylmagnesium chloride, propyl group magnesium chloride, butylmagnesium chloride, amyl group magnesium chloride, phenyl-magnesium-chloride, magnesium dichloride, dibrominated magnesium, diiodinating magnesium, the alcohol adducts of magnesium dichloride, at least one in the alcohol adducts of dibrominated magnesium and the alcohol adducts of diiodinating magnesium.Most preferably, described magnesium compound contains at least one in diethoxy magnesium, butylmagnesium chloride, oxyethyl group magnesium chloride, magnesium dichloride.
Preferred at another, the general formula of described titanium compound is TiX
m(OR
7)
4-m, in formula, X is halogen, R
7for C
1-C
20alkyl, preferred C
1-C
5alkyl, m is the integer of 0-4.Such as: at least one in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium and trichlorine one ethanolato-titanium.Most preferably, described titanium compound is titanium tetrachloride.
In the specific embodiment of catalyst component of the present invention, catalyst component is prepared by following method.
Method one, is suspended in alkoxyl magnesium or Alkoxymagnesium halides in inert diluent and forms suspension, then is mixed with above-mentioned titanium compound, internal electron donor by this suspension and contact to obtain solids dispersion system, is commonly referred to mother liquor.Filtered by mother liquor, gained solid matter is suspended in the solution containing titanium tetrachloride and carries out contact pairs, is commonly referred to titanium process; Then after filtration, washing can obtain catalyst solid constituent of the present invention.
As the object lesson of above-mentioned alkoxyl magnesium, dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two pentyloxy magnesium, two hexyloxy magnesium, two (2-ethyl) hexyloxy magnesium etc. or its mixture can be enumerated, be preferably the mixture of diethoxy magnesium or diethoxy magnesium and other alkoxyl magnesium.The preparation method of this alkoxyl magnesium compound, can be prepared by method well known in the art, MAGNESIUM METAL and fatty alcohol is prepared under a small amount of iodine exists disclosed in patent CN101906017A.
As the object lesson of above-mentioned Alkoxymagnesium halides, methoxyl group magnesium chloride, oxyethyl group magnesium chloride, propoxy-magnesium chloride, butoxy magnesium chloride etc. can be enumerated, preferred oxyethyl group magnesium chloride.The preparation method of this alkoxy magnesium compound, can be prepared by method well known in the art, prepares oxyethyl group magnesium chloride as Grignard reagent butylmagnesium chloride mixed with purity titanium tetraethoxide and tetraethoxy-silicane.
The inert diluent that the formation of the mother liquor in aforesaid method one uses can adopt at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.The consumption of each composition that the formation of mother liquor uses, in every mole of magnesium, the usage quantity 0.5-100 mole of titanium compound, is preferably 1-50 mole; The usage quantity of inert diluent is generally 0.5-100 mole, is preferably 1-50 mole; The total amount of electronic donor compound capable is generally 0.005-10 mole, is preferably 0.01-1 mole.During the formation of mother liquor, the Contact Temperature of described each component is generally-40 ~ 200 DEG C, is preferably-20 ~ 150 DEG C; Be generally 1 minute-20 hours duration of contact, be preferably 5 minutes-8 hours.
In described method one, in described titanium treating processes, use alternative in the solution containing titanium tetrachloride to add inert diluent, as at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene; In described titanium treating processes, use consumption containing each composition in titanium tetrachloride solution, in every mole of magnesium, the usage quantity 0.5-100 mole of titanium compound, is preferably 1-50 mole; The usage quantity of inert diluent is generally 0-100 mole, is preferably 0-50 mole; Titanium number of processes is 0-10 time, preferred 1-5 time.In described titanium treating processes, alternative adds above-mentioned electronic donor compound capable, and wherein internal electron donor consumption is generally 0.005-10 mole, is preferably 0.01-1 mole.Described titanium treatment temp is generally 0 ~ 200 DEG C, is preferably 30 ~ 150 DEG C; Be generally 1 minute-20 hours duration of contact, be preferably 5 minutes-6 hours.
Method two, magnesium dihalide is dissolved in the solvent system that organic epoxy compound thing, organo phosphorous compounds, aliphatic alcohols compound and inert diluent form, with above-mentioned titanium compound, electron donor compound contact reacts after formation homogeneous solution, under precipitation additive exists, separate out solids, form mother liquor; Filtered by mother liquor, gained solid matter is suspended in the solution containing titanium tetrachloride and carries out contact pairs, is below commonly referred to as titanium process; Then after filtration, washing can obtain catalyst solid constituent of the present invention.
The precipitation additive used in method two is not particularly limited, as long as it is shaping that solid particulate can be made to separate out.Adducible example has: at least one in organic acid anhydride, organic acid, ester, ether and ketone.The object lesson of described organic acid anhydride can be diacetyl oxide, Tetra hydro Phthalic anhydride, at least one in Succinic anhydried and MALEIC ANHYDRIDE etc., described organic acid object lesson can be acetic acid, propionic acid, butyric acid, at least one in vinylformic acid and methacrylic acid etc., the object lesson of described ester can be dibutyl phthalate, 2, 4-glycol dibenzoate, 3-ethyl-2, 4-glycol dibenzoate, 2, 3-di-isopropyl-1, 4-butyleneglycol dibenzoate, 3, 5-heptanediol dibenzoate and 4-ethyl-3, at least one in 5-heptanediol dibenzoate, the object lesson of described ether can be methyl ether, ether, propyl ether, butyl ether, amyl ether, 2-sec.-propyl-2-isopentyl Propanal dimethyl acetal and 9, at least one in 9-(dimethoxy methyl) fluorenes, described ketone can be acetone, at least one in methylethylketone and benzophenone.
In method two, the organic epoxy compound thing of described use can for being selected from least one in oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether and diglycidylether etc., preferred epoxy chloropropane.The organo phosphorous compounds of described use can be hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid, the object lesson of this organo phosphorous compounds can be enumerated: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate or phosphorous acid benzene methyl etc., preferred ortho-phosphoric acid tri-n-butyl.The aliphatic alcohols compound of described use can be straight or branched alkane unitary or the multi-alcohol of carbonatoms 1-20, the straight or branched unitary fatty alcohol of preferred carbonatoms 1-10, object lesson can be enumerated: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, hexanol, enanthol, (2-ethyl) hexyl alcohol, octanol, nonyl alcohol, decyl alcohol etc., preferably (2-ethyl) hexyl alcohol.
In method two, the inert diluent that mother liquor forms middle use can adopt at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.Mother liquor forms the consumption of each composition of middle use, and in every mole of magnesium halide, organic epoxy compound thing can be 0.2-10 mole, is preferably 0.5-4 mole; Organo phosphorous compounds can be 0.1-3 mole, is preferably 0.3-1.5 mole; Fat alcohol compound can be 0.2-10 mole, is preferably 0.5-3 mole; Titanium compound can be 0.5-20 mole, is preferably 5-15 mole; Helping and separating out component to be 0.01-0.3 mole, is preferably 0.02-0.2 mole; Electronic donor compound capable total amount can be 0-10 mole, is preferably 0.02-0.3 mole.During the formation of mother liquor, the Contact Temperature of described each component is generally-40 ~ 200 DEG C, is preferably-20 ~ 150 DEG C; Be generally 1 minute-20 hours duration of contact, be preferably 5 minutes-8 hours.
In method two, in described titanium treating processes, use alternative in the solution containing titanium tetrachloride to add inert diluent, as at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.In described titanium treating processes, use consumption containing each composition in titanium tetrachloride solution, in every mole of magnesium, the usage quantity 0.5-100 mole of titanium compound, is preferably 1-50 mole; The usage quantity of inert diluent is generally 0-100 mole, is preferably 0-50 mole.Described titanium number of processes is 0-10 time, preferred 1-5 time.In described titanium treating processes, alternative adds above-mentioned electronic donor compound capable, and wherein internal electron donor consumption is generally 0.005-10 mole, is preferably 0.01-1 mole.Described titanium treatment temp is generally 0 ~ 200 DEG C, is preferably 30 ~ 150 DEG C; Be generally 1 minute-20 hours duration of contact, be preferably 5 minutes-6 hours.
Method three, is suspended in the alcohol adducts of magnesium dihalide in inert diluent and forms suspension, then is mixed with above-mentioned titanium compound, internal electron donor by this suspension and contact to obtain solids dispersion system, is below commonly referred to as mother liquor.Filtered by mother liquor, gained solid matter is suspended in the solution containing titanium tetrachloride and carries out contact pairs, is below commonly referred to as titanium process; Then after filtration, washing can obtain catalyst solid constituent of the present invention.
In method three, the alcohol adducts of described magnesium dihalide can obtain by the following method: under not miscible with adducts inert solvent (as hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene etc.) exists, alcohol (as methyl alcohol, ethanol, propyl alcohol or Virahol etc.) and magnesium halide are mixed to form emulsion, make the rapid chilling dispersion of this emulsion, gained spheroidal particle is the alcohol adducts of magnesium dihalide.
In aforesaid method three, the inert diluent that the formation of mother liquor uses can adopt at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.The consumption of each composition that the formation of mother liquor uses, in every mole of magnesium, the usage quantity 0.5-100 mole of titanium compound, is preferably 1-50 mole; The usage quantity of inert diluent is generally 0.5-100 mole, is preferably 1-50 mole; The total amount of electronic donor compound capable is generally 0.005-10 mole, is preferably 0.01-1 mole.During the formation of mother liquor, the Contact Temperature of described each component is generally-40 ~ 200 DEG C, is preferably-20 ~ 150 DEG C; Be generally 1 minute-20 hours duration of contact, be preferably 5 minutes-8 hours.
In method three, in described titanium treating processes, use alternative in the solution containing titanium tetrachloride to add inert diluent, as at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.In titanium treating processes, use consumption containing each composition in titanium tetrachloride solution, in every mole of magnesium, the usage quantity 0.5-100 mole of titanium compound, is preferably 1-50 mole; The usage quantity of inert diluent is generally 0-100 mole, is preferably 0-50 mole.Titanium number of processes is 0-10 time, preferred 1-5 time.In titanium treating processes, alternative adds above-mentioned electronic donor compound capable, and wherein internal electron donor consumption is generally 0.005-10 mole, is preferably 0.01-1 mole.Titanium treatment temp is generally 0 ~ 200 DEG C, is preferably 30 ~ 150 DEG C; Be generally 1 minute-20 hours duration of contact, be preferably 5 minutes-6 hours.
According to another aspect of the present invention, provide a kind of catalyzer for olefinic polymerization, described catalyzer comprises the reaction product of following component:
A. above-mentioned catalyst component;
B. organo-aluminium compound;
C. optionally, external donor compound.
According to olefin polymerization catalysis of the present invention, the various organo-aluminium compounds that can be used as the promotor of Ziegler-natta catalyst that the organo-aluminium compound as promotor can be commonly used for field of olefin polymerisation.Preferred described organo-aluminium compound is for being general formula AlR'
n'x'
3-n'shown organo-aluminium compound, wherein, R' is selected from hydrogen, C
1-C
20alkyl and C
6-C
20aryl; X' is halogen, and n' is the integer of 1-3.
In above-mentioned catalyzer, at least one of described organo-aluminium compound preferably in following compound: at least one in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride.More preferably triethyl aluminum and/or triisobutyl aluminium.
In above-mentioned catalyzer, the consumption of described organo-aluminium compound can be the conventional amount used of this area.Usually, the mol ratio of the aluminium in described organo-aluminium compound and the titanium in described catalyzer is 5-5000:1; Be preferably 20-1000:1; Be more preferably 50-500:1.
In above-mentioned catalyzer, described " optionally, external donor compound " means that described catalyzer can comprise the reaction product of component a and b, also can comprise the reaction product of component a, b and c.According to olefin polymerization catalysis of the present invention, described external electron donor component can be various external electron donors known in the industry, is not particularly limited.
In above-mentioned catalyzer, described external electron donor is preferably general formula R
1"
m "r
2"
n "si (OR
3")
4-m "-n "shown silicoorganic compound, in formula, R
1" and R
2" identical or different, be selected from independently of one another: halogen, hydrogen atom, C
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
1-C
20haloalkyl; R
3" be selected from C
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
1-C
20haloalkyl; M " and n " is respectively the integer of 0-3, and m "+n " <4.Preferably, described silicoorganic compound are selected from least one in following compound: trimethylmethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxysilane, tertbutyl methyl dimethoxysilane, t-butylethyl dimethoxysilane, tertiary butyl propyldimethoxy-silane, ter /-butylisopropyl dimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopentyl-methyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl dimethoxysilane, two (2-methylcyclopentyl) dimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, propyl trimethoxy silicane, propyl-triethoxysilicane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, butyl trimethoxy silane, butyl triethoxyl silane, trimethoxysilane, isobutyl triethoxy silane, amyltrimethoxysilane, isopentyl Trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, tetramethoxy-silicane, tetraethoxysilane or four butoxy silanes, these silicoorganic compound can individually use, and also two or more can be combinationally used.
According to olefin polymerization catalysis of the present invention, the consumption of external electron donor is not particularly limited.In the preferred case, the mol ratio of the aluminium in described organo-aluminium compound and described external donor compound is 0.1-500:1, preferred 1-300:1, more preferably 3-100:1.Namely, when described external donor compound selects silicoorganic compound, the mol ratio of described organo-aluminium compound and silicoorganic compound counts 0.1:1-500:1 with aluminium/silicon, preferred 1:1-300:1, more preferably 3:1-100:1.
According to another aspect of the present invention, provide a kind of olefine polymerizing process, described alkene is polymerized under the effect of above-mentioned catalyst component or above-mentioned catalyzer.
According to olefine polymerizing process of the present invention, it both can be used for the homopolymerization of alkene, also can be used for the copolymerization of alkene.
According to the present invention, described alkene general formula be CH
2=CHR, R are hydrogen or C
1-C
12alkyl, be preferably hydrogen or C
1-C
6alkyl.As described in alkene be preferably selected from least one in following compound: ethene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene; More preferably at least one in ethene, propylene and 1-butylene is selected from.
According to olefine polymerizing process of the present invention, described olefin polymerization conditions is the temperature of olefinic polymerization is 0-150 DEG C, preferred 60-130 DEG C; Time is 0.1-5 hour, preferred 0.5-4 hour, and pressure is 0.01-10MPa, is preferably 0.5-5MPa.The consumption of catalyzer can be the consumption of the various catalyzer of prior art.
According to the present invention, by the catalyzer adopting the internal electron donor shown in the formula I of novel texture to obtain, with comparing containing phthalate internal electron donor compound (it has been proved the Fertility being unfavorable for people) the most frequently used in prior art, there is higher security; And significantly improve the melting index (meaning the hydrogen regulation performance significantly improving catalyzer) of polymkeric substance and widened molecular weight distribution.According to the present invention, the catalyzer of high comprehensive performance can be obtained, polymerization activity is suitable for, the stereotaxis ability of catalyzer is good and hydrogen response is good; For olefinic polymerization, especially during propylene polymerization, gratifying polymerization yield rate can be obtained, and the tap density of polymkeric substance is high, degree of isotacticity good, melting index is high and molecular weight distribution is wider, is conducive to the exploitation of different trade mark polymkeric substance.According to novel catalyzer provided by the invention, there is excellent over-all properties, there is broad application prospect.
Embodiment
Embodiment given below is used to further illustrate the present invention, but does not form any limitation of the invention.
Testing method:
1, the titanium content in catalyzer: according to 721 spectrophotometer tests.
2, in catalyzer, internal electron donor content uses Agilent6890Series gas Chromatographic Determination.
3, the mensuration of melt index: measure according to GB/T3682-2000.
4, polymkeric substance degree of isotacticity adopts heptane extraction process to measure: 2 grams of dry polymer samples, be placed on seething with excitement heptane extracting after 6 hours in extractor, the ratio of the polymer weight (g) and 2 (g) that residuum are dried to constant weight gained is degree of isotacticity.
5, molecular weight distribution uses Waters company AllianceGPCV2000 gel chromatograph to measure (solvent comprises trichlorobenzene, flow 1.0mL/min measure temperature 433K, standard specimen polystyrene).
One, the synthesis of internal electron donor
Compd A: 2,2 '-biphenyl dicarboxylic acid dimethyl ester
30.0g (0.125mol) biphenyl dicarboxylic acid, 2.0g Tetrabutyl amonium bromide, is dissolved in dried 200mLN, in the mixed solvent of N '-dimethyl methane amide and 100mL acetone, sways to dissolving completely.Add 51.8g (0.375mol) salt of wormwood, rock to basic bubble-free and release.Add 42.6g (0.30mol) methyl iodide, stirring at room temperature 1 hour, 30 DEG C are stirred 4 hours, and 50 DEG C are stirred 8 hours.Reaction terminates, and solids removed by filtration, revolves except clean solvent, adds water 300mL, extraction into ethyl acetate three times, merge organic item, anhydrous magnesium sulfate drying, filter, revolve and desolventize, obtain crude product, normal hexane recrystallization obtains final product 26.4g, productive rate 78%, purity 99.0% (GC).
1HNMR(CDCl
3/TMS,300MHz)δ(ppm):3.610(s,6H,-OCH
3),7.189-7.218(m,2H,C
6H
5-),7.394-7.450(m,2H,C
6H
5-),7.503-7.558(m,2H,C
6H
5-)，7.988-7.922(m,2H,C
6H
5-)。
Compd B: 2,2 '-biphenyl dicarboxylic acid diethyl ester
Use similar method, prepare 2,2 '-biphenyl dicarboxylic acid diethyl ester sterling 21.9g, productive rate 81%, purity 98.4% (LC).
1HNMR(CDCl
3/TMS,300MHz)δ(ppm):0.948-0.995(t,6H,-OCH
2CH
3),3.998-4.070(q,4H,-OCH
2CH
3),7.188-7.213(m,2H,C
6H
5-),7.217-7.446(m,2H,C
6H
5-),7.482-7.532(m,2H,C
6H
5-)，7.988-8.014(m,2H,C
6H
5-)。
Compound C: 2,2 '-biphenyl dicarboxylic acid di-n-butyl
Use similar method, prepare 2,2 '-biphenyl dicarboxylic acid di-n-butyl sterling 32.4g, productive rate 87%, purity 97.2% (GC).
1HNMR(CDCl
3/TMS,300MHz)δ(ppm):0.788-0.837(t,6H,-OCH
2CH
2CH
2CH
3),1.073-1.195(q,4H,-OCH
2CH
2CH
2CH
3),1.276-1.371(q,4H,-OCH
2CH
2CH
2CH
3),3.967-4.010(q,4H,-OCH
2CH
2CH
2CH
3),7.176-7.204(m,2H,C
6H
5-),7.389-7.444(m,2H,C
6H
5-),7.476-7.531(m,2H,C
6H
5-)，7.996-8.026(m,2H,C
6H
5-)。
Compound D: 2,2 '-biphenyl dicarboxylic acid diisobutyl ester
Use similar method, prepare 2, the just different ester sterling 41.6g of 2 '-biphenyl dicarboxylic acid two, productive rate 82%, purity 98.7% (GC).
1HNMR(CDCl
3/TMS,300MHz)δ(ppm):0.715-0.757(m,12H,-OCH
2CH(CH
3)
2),1.571-1.689(m,2H,-OCH
2CH(CH
3)
2),3.780-3.802(d,4H,-OCH
2CH(CH
3)
2),7.180-7.211(m,2H,C
6H
5-),7.384-7.439(m,2H,C
6H
5-),7.478-7.533(m,2H,C
6H
5-)，8.003-8.004(m,2H,C
6H
5-)。
Two, application examples
Embodiment 1
The preparation of magnesium compound
Prepared by alkoxyl magnesium: with in the 1L reactor of agitator, reflux condensing tube, thermometer and drop-burette, after fully replacing, add ethanol 550mL in reactor, Virahol 10mL with nitrogen, iodine 0.68g dissolves.Heat up after opening stirring, until reach the reflux temperature of reaction system.Then magnesium powder 32g is successively added; React to no longer including hydrogen discharge.Then carry out washing, filtering and drying, obtain tap density 0.25g/cm
3, the alkoxyl magnesium 147g of median size (D50) 47.0 μm.
The preparation of catalyst component
Get the electron donor compd A 2.5g of above-mentioned obtained alkoxyl magnesium carrier 10g, toluene 50mL and above-mentioned preparation, be mixed with suspension; In the reactor repeating the 300mL replaced through high pure nitrogen, add toluene 40mL and titanium tetrachloride 60mL, then the suspension prepared is added in still, be warming up to 80 DEG C, constant temperature 1 hour is follow-up is continuously warming up to 115 DEG C, constant temperature after 2 hours by clean for liquid (mother liquor) press filtration.The mixed solution adding toluene 90mL and titanium tetrachloride 60mL is warming up to 110 DEG C of stir process 1 hour (titanium process), by clean for liquid (mother liquor) press filtration, the mixed solution adding toluene 120mL and titanium tetrachloride 30mL is again warming up to 110 DEG C of stir process 2 hours (titanium process), elimination liquid, the solid of gained washs 3 times at 55 DEG C with normal hexane 150mL, room temperature with n-hexane once, elimination liquid is also dry, obtains ingredient of solid catalyst of the present invention.
Propylene polymerization
In a 5L autoclave, after gas-phase propene is fully replaced, at room temperature add the 10mg ingredient of solid catalyst of the hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of 5mL triethyl aluminum, the hexane solution (concentration of CHMMS is 0.10mmol/mL) of lmL Cyclohexyl Methyl Dimethoxysilane (CHMMS), 10mL anhydrous hexane and above-mentioned preparation.Close autoclave, introduce the liquid propene that 4.5 standards rise hydrogen and 2L; In under agitation 10 minutes, temperature is risen to 70 DEG C.At 70 DEG C, polyreaction is after 1 hour, stops stirring, and removes unpolymerized propylene monomer, collected polymer.Data are in table 1.
Embodiment 2-4
Step is with embodiment 1, and difference is to adopt internal electron donor compound B, C and D respectively.Data are in table 1.
Comparative example 1:
Internal electron donor compound, with embodiment 1, is changed to n-butyl phthalate (DNBP) by step.Data are in table 1.
Comparative example 2:
Step, with embodiment 1, just uses diethylene adipate (DEA) as internal electron donor compound.Data are in table 1.
Comparative example 3:
Step, with embodiment 1, just uses Di-n-butyl Adipate (DBA) as internal electron donor compound.Data are in table 1.
Comparative example 4:
Step, with embodiment 1, just uses diisobutyl adipate (DIA) as internal electron donor compound.Data are in table 1.
The performance of table 1. catalyzer
A: the mass percent referring to internal electron donor in catalyzer, by gas Chromatographic Determination.
N.A.: refer to, because activity is too low, do not have practical significance, this parameter does not characterize.
As can be seen from Table 1, use catalyzer prepared by the catalyst component comprising ad hoc structure internal electron donor of the present invention, with comparing containing n-butyl phthalate the most frequently used in prior art, not only increase the security of catalyzer, and significantly improve the melting index (meaning the hydrogen regulation performance that improve catalyzer) of polymkeric substance and widened molecular weight distribution.The advantage that catalyst according to the invention has that hydrogen regulation performance is good, polymerization activity is suitable for and stereotaxis ability is good etc.; During for olefinic polymerization, the polymkeric substance obtained has good degree of isotacticity, higher melting index, wider molecular weight distribution and higher tap density.Especially there is high melting index, mean that catalyzer has good hydrogen regulation performance, be suitable for the exploitation of specific acrylic resin.According to novel catalyzer provided by the invention, there is excellent over-all properties, there is broad application prospect.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (12)
1. a catalyst component for olefin, comprises the internal electron donor compound shown in titanium, halogen, magnesium and formula I,
In formula, R
1and R
2can be identical or not identical, be selected from substituted or unsubstituted C independently of one another
1-C
20alkyl, be preferably selected from substituted or unsubstituted C
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl and C
7-C
20aralkyl; R
3-R
10can be identical or not identical, be selected from hydrogen and substituted or unsubstituted C independently of one another
1-C
20alkyl, be preferably selected from hydrogen and substituted or unsubstituted C
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
7-C
20alkaryl; R
3-R
10optionally connect into ring or not Cheng Huan.
2. catalyst component according to claim 1, is characterized in that, described R
1and R
2be selected from substituted or unsubstituted C
1-C
10alkyl, C
3-C
10cycloalkyl, C
6-C
10aryl, C
7-C
10aralkyl and C
7-C
10alkaryl; Described R
3-R
10be selected from hydrogen and substituted or unsubstituted C
1-C
10alkyl, C
3-C
10cycloalkyl and C
6-C
10aryl.
3. catalyst component according to claim 1 and 2, is characterized in that, described R
1and R
2be selected from substituted or unsubstituted C
1-C
8alkyl, phenyl, C
7-C
10alkyl phenyl and C
7-C
10alkoxyl phenyl; Described R
3-R
10be selected from hydrogen and substituted or unsubstituted C
1-C
6alkyl.
4. according to the catalyst component in claim 1-3 described in any one, it is characterized in that, the internal electron donor compound shown in described formula I is selected from 2,2 '-biphenyl dicarboxylic acid dimethyl ester, 2,2 '-biphenyl dicarboxylic acid diethyl ester, 2,2 '-biphenyl dicarboxylic acid di-n-propyl ester, 2,2 '-biphenyl dicarboxylic acid diisopropyl ester, 2,2 '-biphenyl dicarboxylic acid di-n-butyl, 2,2 '-biphenyl dicarboxylic acid diisobutyl ester, 2,2 '-biphenyl dicarboxylic acid two (1-methyl) propyl ester, 2,2 '-biphenyl dicarboxylic acid di tert butyl carbonate, 2,2 '-biphenyl dicarboxylic acid two n-pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (1-methyl) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (2-methyl) butyl ester, 2,2 '-biphenyl dicarboxylic acid diisoamyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 '-dimethyl) propyl ester, 2, the special pentyl ester of 2 '-biphenyl dicarboxylic acid two, 2,2 '-biphenyl dicarboxylic acid two (1,2-dimethyl) propyl ester, 2, the just own ester of 2 '-biphenyl dicarboxylic acid, 2,2 '-biphenyl dicarboxylic acid two (1-methyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (2-methyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (3-methyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two dissident ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 '-dimethyl) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,2 '-dimethyl) butyl ester, 2, the special own ester of 2 '-biphenyl dicarboxylic acid two, 2,2 '-biphenyl dicarboxylic acid two (1,2-dimethyl) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,3-dimethyl) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,3-dimethyl) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 2-trimethylammonium) propyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,2,2 '-trimethylammonium) propyl ester, 2, the positive heptyl ester of 2 '-biphenyl dicarboxylic acid, 2,2 '-biphenyl dicarboxylic acid two (1-methyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (2-methyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (3-methyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (4-methyl) own ester, 2,2 '-biphenyl dicarboxylic acid two isocyanate, 2,2 '-biphenyl dicarboxylic acid two (1,1 '-dimethyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,2 '-dimethyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (3,3 '-dimethyl) pentyl ester, 2, the special heptyl ester of 2 '-biphenyl dicarboxylic acid two, 2,2 '-biphenyl dicarboxylic acid two (1,2-dimethyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,3-dimethyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (Isosorbide-5-Nitrae-dimethyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,3-dimethyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,4-dimethyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (3,4-dimethyl) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 2-trimethylammonium) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 3-trimethylammonium) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,2,2 '-trimethylammonium) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,2 ', 3-trimethylammonium) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,3,3 '-trimethylammonium) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,3,3 '-trimethylammonium) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 2,2 '-tetramethyl-) propyl ester, 2,2 '-biphenyl dicarboxylic acid n-octyl, 2,2 '-biphenyl dicarboxylic acid two (1-methyl) heptyl ester, 2,2 '-biphenyl dicarboxylic acid two (2-methyl) heptyl ester, 2,2 '-biphenyl dicarboxylic acid two (3-methyl) heptyl ester, 2,2 '-biphenyl dicarboxylic acid two (4-methyl) heptyl ester, 2,2 '-biphenyl dicarboxylic acid two (5-methyl) heptyl ester, 2,2 '-biphenyl dicarboxylic acid di-isooctyl, 2,2 '-biphenyl dicarboxylic acid two (1,1 '-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (2,2 '-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (3,3 '-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (4,4 '-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (5,5 '-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (1,2-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (1,3-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (Isosorbide-5-Nitrae-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (1,5-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (2,3-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (2,4-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (2,5-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (3,4-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (3,5-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (4,5-dimethyl) own ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 2-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 3-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 4-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,2,2 '-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,2 ', 3-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,2 ', 4-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,3,3 '-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,3,3 '-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (3,3 ', 4-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (Isosorbide-5-Nitrae, 4 '-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,4,4 '-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (3,4,4 '-trimethylammonium) pentyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 2,2 '-tetramethyl-) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (1,1 ', 3,3 '-tetramethyl-) butyl ester, 2,2 '-biphenyl dicarboxylic acid two (2,2 ', 3,3 '-tetramethyl-) butyl ester, 2,2 '-diphenyl bibenzoate, 2,2 '-biphenyl dicarboxylic acid two (adjacent methyl) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (to methyl) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (methyl) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (O-methoxy) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (to methoxyl group) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (meta-methoxy) phenyl ester, be preferably selected from 2,2 '-biphenyl dicarboxylic acid dimethyl ester, 2,2 '-biphenyl dicarboxylic acid diethyl ester, 2,2 '-biphenyl dicarboxylic acid di-n-propyl ester, 2,2 '-biphenyl dicarboxylic acid diisopropyl ester, 2,2 '-biphenyl dicarboxylic acid di-n-butyl, 2,2 '-biphenyl dicarboxylic acid diisobutyl ester, 2,2 '-biphenyl dicarboxylic acid di tert butyl carbonate, 2,2 '-biphenyl dicarboxylic acid two n-pentyl ester, 2,2 '-biphenyl dicarboxylic acid diisoamyl ester, 2, the just own ester of 2 '-biphenyl dicarboxylic acid, 2,2 '-biphenyl dicarboxylic acid two dissident ester, 2, the positive heptyl ester of 2 '-biphenyl dicarboxylic acid, 2,2 '-biphenyl dicarboxylic acid isocyanate, 2,2 '-biphenyl dicarboxylic acid n-octyl, 2, the different monooctyl ester of 2 '-biphenyl dicarboxylic acid, 2,2 '-diphenyl bibenzoate, 2,2 '-biphenyl dicarboxylic acid two (adjacent methyl) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (to methyl) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (methyl) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (O-methoxy) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (to methoxyl group) phenyl ester, 2,2 '-biphenyl dicarboxylic acid two (meta-methoxy) phenyl ester, more preferably 2 are selected from, 2 '-biphenyl dicarboxylic acid dimethyl ester, 2, 2 '-biphenyl dicarboxylic acid diethyl ester, 2, 2 '-biphenyl dicarboxylic acid di-n-propyl ester, 2, 2 '-biphenyl dicarboxylic acid diisopropyl ester, 2, 2 '-biphenyl dicarboxylic acid di-n-butyl, 2, 2 '-biphenyl dicarboxylic acid diisobutyl ester, 2, 2 '-biphenyl dicarboxylic acid di tert butyl carbonate, 2, 2 '-biphenyl dicarboxylic acid two n-pentyl ester, 2, 2 '-biphenyl dicarboxylic acid diisoamyl ester, 2, the just own ester of 2 '-biphenyl dicarboxylic acid, 2, 2 '-biphenyl dicarboxylic acid dissident ester, 2, 2 '-diphenyl bibenzoate, 2, 2 '-biphenyl dicarboxylic acid two (adjacent methyl) phenyl ester, 2, 2 '-biphenyl dicarboxylic acid two (to methyl) phenyl ester, 2, 2 '-biphenyl dicarboxylic acid two (O-methoxy) phenyl ester, 2, 2 '-biphenyl dicarboxylic acid two (to methoxyl group) phenyl ester.
5. according to the catalyst component in claim 1-4 described in any one, it is characterized in that, the content of described titanium is 1.0-8.0wt%, is preferably 1.6-6.0wt%; The content of magnesium is 10-70wt%, is preferably 15-40wt%; The content of halogen is 20-90wt%, is preferably 30-85%; Internal electron donor compound content is 2-30wt%, is preferably 3-20wt%.
6., according to the catalyst component in claim 1-5 described in any one, it comprises the internal electron donor shown in magnesium compound, titanium compound and formula I is carried out catalytic product in a solvent.
7. catalyst component according to claim 6, is characterized in that, described magnesium compound is selected from formula M gR
4r
5shown magnesium compound, formula M gR
4r
5pH
2the hydrate of the magnesium compound shown in O and formula M gR
4r
5qR
6the alcohol adducts of the magnesium compound shown in OH, in general formula, R
4and R
5be selected from halogen, C independently of one another
1-C
8the alkoxyl group of straight or branched and C
1-C
8straight or branched alkyl; P and q is separately selected from 0.1-6, preferred 2-3.5; R
6for C
1-C
18alkyl, be preferably C
1-C
8alkyl, be more preferably selected from methyl, ethyl, n-propyl and sec.-propyl.
8. the catalyst component according to claim 6 or 7, is characterized in that, the general formula of described titanium compound is TiX
m(OR
7)
4-m, in formula, X is halogen, R
7for C
1-C
20alkyl, preferred C
1-C
5alkyl, m is the integer of 0-4, most preferably is titanium tetrachloride.
9., for a catalyzer for olefinic polymerization, it comprises the reaction product of following component:
A. the catalyst component in claim 1-8 described in any one;
B. organo-aluminium compound, is preferably general formula AlR'
n'x'
3-n'shown organo-aluminium compound, wherein, R' is selected from hydrogen, C
1-C
20alkyl and C
6-C
20aryl; X' is halogen, and n' is the integer of 1-3;
C. optionally, external donor compound, is preferably general formula R
1"
m "r
2"
n "si (OR
3")
4-m "-n "shown silicoorganic compound, in formula, R
1" and R
2" identical or different, be selected from independently of one another: halogen, hydrogen atom, C
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
1-C
20haloalkyl; R
3" be selected from C
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
1-C
20haloalkyl; M " and n " is respectively the integer of 0-3, and m "+n " <4.
10. catalyzer according to claim 9, it is characterized in that, the mol ratio of described organo-aluminium compound and catalyst solid constituent counts 5:1-5000:1 with aluminium/titanium, is preferably 20:1-1000:1, is more preferably 50:1-500:1; Aluminium in described organo-aluminium compound and the mol ratio of external donor compound are 0.1:1-500:1, preferred 1:1-300:1, more preferably 3:1-100:1.
11. 1 kinds of olefine polymerizing process, are polymerized under the effect of described alkene catalyzer described in catalyst component described in any one or claim 9 or 10 in claim 1-8.
12. methods according to claim 11, is characterized in that, the general formula of described alkene is CH
2=CHR, R are hydrogen or C
1-C
12alkyl, be preferably hydrogen or C
1-C
6alkyl, be preferably selected from ethene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene, be more preferably selected from ethene, propylene and 1-butylene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108517021A (en) * | 2017-03-10 | 2018-09-11 | 北京利和知信科技有限公司 | A kind of ingredient of solid catalyst, catalyst and its application being suitable for producing broad molecular weight distribution polymers |
| WO2018161854A1 (en) * | 2017-03-10 | 2018-09-13 | 北京利和知信科技有限公司 | Solid catalyst component for use in olefin polymerisation, catalyst, and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597714A (en) * | 2003-09-18 | 2005-03-23 | 中国石油化工股份有限公司 | Method of producing olefine polymer and its polymer |
| KR20120077678A (en) * | 2010-12-31 | 2012-07-10 | 주식회사 효성 | Catalysts for polymerization or copolymerization of olefins, its preparing method and olefins polymerization or copolymerization method |
| CN102712704A (en) * | 2009-12-02 | 2012-10-03 | 陶氏环球技术有限责任公司 | Three and four atom bridged dicarbonate compounds as internal donors in catalysts for polypropylene manufacture |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597714A (en) * | 2003-09-18 | 2005-03-23 | 中国石油化工股份有限公司 | Method of producing olefine polymer and its polymer |
| CN102712704A (en) * | 2009-12-02 | 2012-10-03 | 陶氏环球技术有限责任公司 | Three and four atom bridged dicarbonate compounds as internal donors in catalysts for polypropylene manufacture |
| KR20120077678A (en) * | 2010-12-31 | 2012-07-10 | 주식회사 효성 | Catalysts for polymerization or copolymerization of olefins, its preparing method and olefins polymerization or copolymerization method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108517021A (en) * | 2017-03-10 | 2018-09-11 | 北京利和知信科技有限公司 | A kind of ingredient of solid catalyst, catalyst and its application being suitable for producing broad molecular weight distribution polymers |
| WO2018161854A1 (en) * | 2017-03-10 | 2018-09-13 | 北京利和知信科技有限公司 | Solid catalyst component for use in olefin polymerisation, catalyst, and application thereof |
| CN108517021B (en) * | 2017-03-10 | 2020-10-27 | 北京利和知信科技有限公司 | Solid catalyst component suitable for producing polymer with wide molecular weight distribution, catalyst and application thereof |
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