CN105085746A - Catalyst component for propylene polymerization, and catalyst thereof - Google Patents
Catalyst component for propylene polymerization, and catalyst thereof Download PDFInfo
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- CN105085746A CN105085746A CN201410168507.8A CN201410168507A CN105085746A CN 105085746 A CN105085746 A CN 105085746A CN 201410168507 A CN201410168507 A CN 201410168507A CN 105085746 A CN105085746 A CN 105085746A
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- benzoyloxy
- ethylpyridine
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Abstract
The present invention provides a catalyst component for propylene polymerization, wherein the catalyst component contains magnesium, titanium, halogen and an internal electron donor, the internal electron donor is a composite internal electron donor of a compound represented by a general formula I and a diol ester compound, the structure of the compound represented by the general formula I is defined in the specification, and in the general formula I, R and R<'> are the same or different, and are substituent-containing or substituent-free C1-C20 alkyl, C2-C20 alkenyl, or heteroatom-containing or heteroatom-free C6-C20 aryl, the substituent is selected from hydrocarbyl, hydroxy and halogen, the heteroatom is N, R1-R5 are the same or different, and are hydrogen, halogen atoms, hydroxyl, alkoxy or substituent-containing or substituent-free C1-C12 alkyl, C2-C12 alkenyl or C6-C20 aryl, and X is carbon or nitrogen. The invention further correspondingly provides a catalyst. According to the present invention, the obtained catalyst has high activity and high directing capability, and the molecular weight distribution of the obtained polymer is wide.
Description
Technical field
The present invention relates to propylene polymerization field, be specifically related to a kind of Ziegler-Natta catalyst component for propylene polymerization and catalyzer thereof.
Background technology
Ziegler-Natta catalyst is catalyzer the most frequently used in propylene polymerization.For traditional propylene polymerization Ziegler-Natta catalyst, along with the development of the electron donor compound in catalyzer, catalyzer also constantly updates.The research and development of catalyzer are from the TiCl of the first-generation
3alCl
3/ AlEt
2the TiCl of Cl system and the s-generation
3/ AlEt
2cl system, the magnesium chloride to the third generation is carrier, monoesters or aromatic dibasic acid ester are internal electron donor, silane is the TiCl of external electron donor
4eDMgCl
2/ AlR
3eD system, the active and gained polypropylene degree of isotacticity height of the catalytic polymerization of catalyzer is all greatly improved, and two ethers newly developed, diester class are the catalyst system of internal electron donor.In the prior art, for the titanium catalyst system of propylene polymerization mainly with magnesium, titanium, halogen and electron donor as basal component, wherein electron donor compound is one of requisite component in catalyst component.At present, disclose multiple electron donor compound, as monocarboxylic ester or multi-carboxylate, acid anhydrides, ketone, monoether or polyether, alcohol, amine etc. and derivative thereof, wherein comparatively conventional is aromatic dicarboxylic acids's ester class, such as n-butyl phthalate or diisobutyl phthalate etc., can see US Patent No. 4784983.Disclosed in US Patent No. 4971937 and European patent EP 0728769 in the component of olefin polymerization catalyst, it is special in 1 of two ether groups to have employed, 3-diether compound is electron donor, as 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal and 9,9-bis-(methoxyl methyl) fluorenes etc.Thereafter the dibasic aliphatic carboxylic acid ester compound that a class is special is again disclosed, as (see WO98/56830, WO98/56834, WO01/57099, WO01/63231 and WO00/55215) such as succinate, malonic ester, glutarates, the use of this kind of electron donor compound not only can improve the activity of catalyzer, and the molecular weight distribution of gained propene polymer is obviously widened.
But this area still needs to make improvements Ziegler-Natta catalyst and catalyst component thereof, to make it have higher catalyst activity and orientation property, and make the molecular weight distribution of resulting polymers wider.
Summary of the invention
The object of the invention is to a kind of catalyzer for propylene polymerization of development and component thereof.Contriver finds, by increase on existing internal electron donor basis a kind of as shown in general formula I compound be compound internal electron donor form novel catalytic polymerization system time, gained catalyzer has higher activity and orientation property, and the molecular weight distribution of resulting polymers is wider.
Therefore, the invention provides a kind of catalyst component for propylene polymerization, containing magnesium, titanium, halogen and internal electron donor in described catalyst component, and the compound internal electron donor that described internal electron donor is compound shown in general formula I and dibasic alcohol ester compound, shown in general formula I, compound structure is as follows
In general formula I, R and R ' is identical or different, for containing substituting group or not containing substituent C
1~ C
20alkyl, C
2~ C
20thiazolinyl or C
6~ C
20containing or not containing heteroatomic aryl, and described substituting group is selected from alkyl, hydroxyl and halogen, described heteroatoms is N;
R
1~ R
5identical or different, be hydrogen, halogen atom, hydroxyl, alkoxyl group or containing substituting group or not containing substituent C
1~ C
12alkyl, C
2~ C
12thiazolinyl or C
6~ C
20aryl;
X is carbon or nitrogen.
Preferred dibasic alcohol ester compound of the present invention is such as compound shown in general formula I I,
In general formula I I, R
1and R
2identical or different, for the C of halogen substiuted or unsubstituted straight chain, side chain or ring-type
1~ C
20alkyl; R
3~ R
6identical or different, be hydrogen, halogen atom, hydroxyl, alkoxyl group or containing substituting group or not containing substituent C
1~ C
12alkyl, C
2~ C
12thiazolinyl or C
6~ C
20aryl, and R
3~ R
6between two or more groups can connect into ring; R
iand R
iIidentical or different, be the C of hydrogen or straight chain, side chain or ring-type
1~ C
20alkyl, R
iand R
iIbetween can connect into ring; N is the integer of 0 ~ 10.
In a kind of concrete embodiment, described dibasic alcohol ester compound is selected from 2-sec.-propyl-1,3-bis-benzoyloxy propane, 2-butyl-1,3-bis-benzoyloxy propane, 2-cyclohexyl-1,3-bis-benzoyloxy propane, 2-benzyl-1,3-bis-benzoyloxy propane, 2-phenyl-1,3-bis-benzoyloxy propane, 2-(1-naphthyl)-1,3-bis-benzoyloxy propane, 2-sec.-propyl-1,3-diethyl carboxyl propane, 2-sec.-propyl-2-isopentyl-1,3-bis-benzoyloxy propane, 2-sec.-propyl-2-isobutyl--1,3-bis-benzoyloxy propane, 2-sec.-propyl-2-isopentyl-1,3-dipropyl carboxyl propane, 2-sec.-propyl-2-butyl-1,3-bis-benzoyloxy propane, 2-sec.-propyl-2-isopentyl-1-benzoyloxy-3-fourth carboxyl propane, 2-sec.-propyl-2-isopentyl-1-benzoyloxy-3-Chinese cassia tree carboxyl propane, 2-sec.-propyl-2-isopentyl-1-benzoyloxy-3-second carboxyl propane, 2,2-bicyclopentyl-1,3-bis-benzoyloxy propane, 2,2-dicyclohexyl-1,3-bis-benzoyloxy propane, 2,2-dibutyl-1,3-bis-benzoyloxy propane, 2,2-diisobutyl-1,3-bis-benzoyloxy propane, 2,2-di-isopropyl-1,3-bis-benzoyloxy propane, 2,2-diethyl-1,3-bis-benzoyloxy propane, 2-ethyl-2-butyl-1,3-bis-benzoyloxy propane, 2,4-bis-benzoyloxy pentane, 3-ethyl-2,4-bis-benzoyloxy pentane, 3-methyl-2,4-bis-benzoyloxy pentane, 3-propyl group-2,4-bis-benzoyloxy pentane, 3-sec.-propyl-2,4-bis-benzoyloxy pentane, 2,4-bis-(2-propylbenzene carboxyphenyl) pentane, 2,4-bis-(4-propylbenzene carboxyphenyl) pentane, 2,4-bis-(2,4-dimethyl benzene carboxyphenyl) pentane, 2,4-bis-(2,4 dichloro benzene carboxyphenyl) pentane, 2,4-bis-(4-chlorobenzene carboxyphenyl) pentane, 2,4-bis-(4-isopropyl benzene carboxyphenyl) pentane, 2,4-bis-(4-butylbenzene carboxyphenyl) pentane, 2,4-bis-(4-isobutyl-benzene carboxyphenyl) pentane, 3,5-bis-benzoyloxy heptane, 4-ethyl-3,5-bis-benzoyloxy heptane, 4-propyl group-3,5-bis-benzoyloxy heptane, 4-sec.-propyl-3,5-bis-benzoyloxy heptane, 3,5-bis-(4-propylbenzene carboxyphenyl) heptane, 3,5-bis-(4-isopropyl benzene carboxyphenyl) heptane, 3,5-bis-(4-isobutyl-benzene carboxyphenyl) heptane, 3,5-bis-(4-butylbenzene carboxyphenyl) heptane, 2-benzoyloxy-4-(4-isobutyl-benzene carboxyphenyl) pentane, 2-benzoyloxy-4-(4-butylbenzene carboxyphenyl) pentane, 2-benzoyloxy-4-(4-propylbenzene carboxyphenyl) pentane, 3-benzoyloxy-5-(4-isobutyl-benzene carboxyphenyl) heptane, 3-benzoyloxy-5-(4-butylbenzene carboxyphenyl) heptane, 3-benzoyloxy-5-(4-propylbenzene carboxyphenyl) heptane, 9,9-bis-benzoyloxy methyl fluorenes, 9,9-dipropyl carboxymethyl group fluorenes, 9,9-bis-isobutyl carboxymethyl group fluorenes, 9,9-bis-fourth carboxymethyl group fluorenes, 9,9-bis-benzoyloxy methyl-4-tertiary butyl fluorenes, 9,9-bis-benzoyloxy methyl-4-propyl group fluorenes, 9,9-bis-benzoyloxy methyl isophthalic acid, 2,3,4-tetrahydrochysene fluorenes, 9,9-bis-benzoyloxy methyl isophthalic acid, 2,3,4,5,6,7,8-octahydro fluorenes, 9,9-bis-benzoyloxy methyl-2,3,6,7-bis-phenylpropyl alcohol indenes, 9,9-bis-benzoyloxy methyl isophthalic acid, 8-dichloro fluorenes, 7,7-bis-benzoyloxy methyl-2,5-norbornadiene, Isosorbide-5-Nitrae-two benzoyloxy butane, 2,3-di-isopropyl-Isosorbide-5-Nitrae-two benzoyloxy butane, 2,3-dibutyl-Isosorbide-5-Nitrae-two benzoyloxy butane, 1,2-bis-benzoyloxy benzene, 3-ethyl-1,2-bis-benzoyloxy benzene, 4-butyl-1,2-bis-benzoyloxy benzene, 1,8-bis-benzoyloxy naphthalene, 2-ethyl-1,8-bis-benzoyloxy naphthalene, 2-propyl group-1,8-bis-benzoyloxy naphthalene, 2-butyl-1,8-bis-benzoyloxy naphthalene, 4-butyl-1,8-bis-benzoyloxy naphthalene, 4-isobutyl--1,8-bis-benzoyloxy naphthalene, 4-sec.-propyl-1,8-bis-benzoyloxy naphthalene, one or more in 4-propyl group-1,8-bis-benzoyloxy naphthalene.
In the present invention, described in R and R ' of preferred formula I, be selected from pyridyl, pyrryl, pyrimidyl and quinolyl containing heteroatomic aryl.
In a kind of concrete embodiment of the present invention, compound shown in general formula I is selected from 2,6-bis-(2,6-imino dimethyl benzene) ethylpyridine, 2,6-bis-(2,6-di-isopropyl phenyl imido) ethylpyridine, 2,6-bis-(phenyl imido) ethylpyridine, 2,6-bis-(2-naphthalene imido grpup) ethylpyridine, 2,6-bis-(1-naphthalene imido grpup) ethylpyridine, 2,6-bis-(fourth imido grpup) ethylpyridine, 2,6-bis-(own imido grpup) ethylpyridine, 2,6-bis-(penta imido grpup) ethylpyridine, 2,6-bis-(pungent imido grpup) ethylpyridine, 2,6-bis-(benzyl imido grpup) ethylpyridine, 2,6-bis-(4-chlorobenzene imido grpup) ethylpyridine, 2,6-bis-(4-trifluoromethyl phenyl imido) ethylpyridine, 2,6-bis-(2-trifluoromethyl phenyl imido) ethylpyridine, 2,6-bis-(2-chloro-6-hydroxybenzene imido grpup) ethylpyridine, 2,6-bis-(8-quinoline imido grpup) ethylpyridine, 2,6-bis-(4-quinoline imido grpup) ethylpyridine, 2,6-bis-(3-quinoline imido grpup) ethylpyridine, 2,6-bis-(2,4,6-Three methyl Benzene imido grpup) ethylpyridine, 2-(phenyl imido) ethyl-6-(2,6-imino dimethyl benzene) ethylpyridine, 2-(phenyl imido) ethyl-6-(2,6-di-isopropyl phenyl imido) ethylpyridine, 2-(phenyl imido) ethyl-6-(to chlorobenzene imido grpup) ethylpyridine, 2-(2,6-di-isopropyl phenyl imido) ethyl-6-(2,6-imino dimethyl benzene) ethylpyridine, 2-(to chlorobenzene imido grpup) ethyl-6-(2,6-di-isopropyl phenyl imido) ethylpyridine, 2-(2-hydroxyl-4-chlorobenzene imido grpup) ethyl-6-(to chlorobenzene imido grpup) ethylpyridine, 2,6-bis-(2-hydroxybenzene imido grpup) ethylpyridine, 2,6-bis-(2-ethylbenzene imido grpup) ethylpyridine, 2,6-bis-(4-ethylbenzene imido grpup) ethylpyridine, 2,6-bis-(2-propylbenzene imido grpup) ethylpyridine, 2,6-bis-(4-propylbenzene imido grpup) ethylpyridine, 2,6-bis-(2-butylbenzene imido grpup) ethylpyridine, 2,6-bis-(4-butylbenzene imido grpup) ethylpyridine, 2,6-bis-(2,6-imino dimethyl benzene) ethylbenzene, one or more in 2,6-bis-(2,6-di-isopropyl phenyl imido) ethylbenzene.
In the present invention's embodiment, the weight percentage of compound shown in general formula I in described catalyst component is 0.01 ~ 20%, be preferably 1 ~ 15%, be more preferably 2 ~ 10%; The weight percentage of described dibasic alcohol ester compound in described catalyst component is 0.01 ~ 20%, is preferably 1 ~ 15%.
The present invention also provides a kind of catalyzer, comprises component a as described below and b, and selectable amount of component b, wherein:
A: catalyst component as above,
B: promotor organo-aluminium compound,
C: external electron donor silicoorganic compound.
Above-mentioned catalyst component can adopt following methods to prepare:
Method 1: homogeneous solution magnesium halide being dissolved in organic epoxy compound thing and organo phosphorous compounds, also can add inert diluent.Above-mentioned homogeneous solution mixes with titanium tetrahalide or derivatives thereof, and when there being precipitation additive to exist in reaction system, just has solids to separate out.The compound of described general formula I and general formula I I is attached on solids, then with titanium tetrahalide or inert diluent process, then uses described compound of Formula I process, obtain the solid catalyst comprising the compositions such as titanium, magnesium, halogen, electron donor.
Method 2: by magnesium halide or organo-magnesium compound, alcohol compound and titanate ester or halogenated titanium compound abundant mix and blend in inert solvent, after heating, cooling obtains ball-type carrier alkoxyl magnesium or alkoxy-magnesium chloride or adds inert solvent obtaining uniform alcohol adduct solution.Above-mentioned carrier or homogeneous solution are mixed with titanium tetrahalide or derivatives thereof, maintain for some time post-heating under low temperature to heat up, add the compound of described general formula I and II, then with titanium tetrahalide or inert diluent process, the solid catalyst comprising the compositions such as titanium, magnesium, halogen, electron donor after eventually passing filtration, washing, drying, is obtained.
Method 3: homogeneous solution magnesium halide being dissolved in organic epoxy compound thing and organo phosphorous compounds, also can add inert diluent, adds the compound of described general formula I and II.Above-mentioned solution is mixed with titanium tetrahalide or derivatives thereof, maintain for some time post-heating under low temperature to heat up, again with titanium tetrahalide or inert diluent process, obtain finally by after filtration, washing, drying the solid catalyst comprising the compositions such as titanium, magnesium, halogen, electron donor.
Method 4: homogeneous solution magnesium halide being dissolved in organic epoxy compound thing and organo phosphorous compounds, also can add inert diluent.Above-mentioned homogeneous solution mixes with titanium tetrahalide or derivatives thereof, and when there being precipitation additive to exist in reaction system, just has solids to separate out.The compound of described general formula I I is attached on solids, described compound of Formula I process is used again after titanium tetrahalide process, then use inert diluent process, obtain finally by after filtration, washing, drying the solid catalyst comprising the compositions such as titanium, magnesium, halogen, electron donor.
When catalyzer of the present invention is used for catalyzing propone polyreaction, catalyst activity is high, and the isotactic index of resulting polymers is high, and catalyst activity decay is slow, and the molecular weight distribution of resulting polymers is wider.
Embodiment
(1) synthesis of compound shown in general formula I
Embodiment 1: the synthesis of compound 2,6-bis-(phenyl imido) ethylpyridine
In the there-necked flask of 250 milliliters, nitrogen adds the DAP of 1.63 grams, the Virahol of 80 milliliters and 0.2 milliliter of Glacial acetic acid after blowing row, stirred at ambient temperature is even.Slowly be added dropwise to the 1.86 grams of aniline be dissolved in 20 milliliters of aqueous isopropanols under room temperature, add rear stirring reaction after 2 hours temperature rising reflux react 48 hours.Reaction soln, through concentrating under reduced pressure, obtains 2.16 grams of (productive rate 69%) products after crossing column chromatography for separation.
1h-NMR (δ, ppm, TMS, CDCl
3): 8.41 ~ 8.46 (2H, m, ArH), 7.96 (1H, m, ArH), 7.05 ~ 7.26 (10H, m, ArH), 2.20 ~ 2.30 (6H, s, CH
3); Mass spectrum, FD-massspectrometry:313.
Embodiment 2: the synthesis of compound 2,6-bis-(to chlorobenzene imido grpup) ethylpyridine
In the there-necked flask of 250 milliliters, nitrogen adds the DAP of 1.63 grams, the Virahol of 80 milliliters and 0.2 milliliter of Glacial acetic acid after blowing row, stirred at ambient temperature is even.Slowly be added dropwise to the 2.44 grams of p-Chlorobenzoic acid amide be dissolved in 20 milliliters of aqueous isopropanols under room temperature, add rear stirring reaction after 2 hours temperature rising reflux react 60 hours.Reaction soln, through concentrating under reduced pressure, obtains 2.16 grams of (productive rate 69%) products after crossing column chromatography for separation.
1h-NMR (δ, ppm, TMS, CDCl
3): 8.31 ~ 8.38 (2H, m, ArH), 7.96 (1H, m, ArH), 7.12 ~ 7.46 (8H, m, ArH), 2.20 ~ 2.30 (6H, s, CH
3); Mass spectrum, FD-massspectrometry:381.
Embodiment 3: the synthesis of compound 2,6-bis-(2,6-di-isopropyl phenyl imido) ethylpyridine
In the there-necked flask of 250 milliliters, nitrogen adds the DAP of 1.63 grams, the Virahol of 80 milliliters and 0.3 milliliter of Glacial acetic acid after blowing row, stirred at ambient temperature is even.Slowly be added dropwise to the 3.56 grams of 2,6-DIPAs be dissolved in 20 milliliters of aqueous isopropanols under room temperature, add rear stirring reaction after 2 hours temperature rising reflux react 72 hours.Reaction soln, through concentrating under reduced pressure, obtains 3.61 grams of (productive rate 75%) products after column chromatography for separation.
1h-NMR (δ, ppm, TMS, CDCl3): 8.28 ~ 8.45 (2H, m, ArH), 7.96 (1H, m, ArH), 7.05 ~ 7.36 (6H, m, ArH), 2.76 ~ 2.82 (4H, m, CH), 2.18 ~ 2.27 (6H, s, CH
3), 1.13 ~ 1.37 (24H, m, CH
3); Mass spectrum, FD-massspectrometry:481.Embodiment 4: the synthesis of compound 2,6-bis-(2,6-imino dimethyl benzene) ethylpyridine
In the there-necked flask of 250 milliliters, nitrogen adds the DAP of 1.63 grams, the Virahol of 80 milliliters and 0.3 milliliter of Glacial acetic acid after blowing row, stirred at ambient temperature is even.Slowly be added dropwise to 2.45 gram of 2, the 6-xylidine be dissolved in 20 milliliters of aqueous isopropanols under room temperature, add rear stirring reaction after 2 hours temperature rising reflux react 68 hours.Reaction soln, through concentrating under reduced pressure, obtains 2.58 grams of (productive rate 70%) products after column chromatography for separation.
1h-NMR (δ, ppm, TMS, CDCl
3): 8.31 ~ 8.42 (2H, m, ArH), 7.93 (1H, m, ArH), 7.06 ~ 7.27 (6H, m, ArH), 2.21 ~ 2.27 (6H, s, CH
3), 2.01 ~ 2.18 (12H, m, CH
3); Mass spectrum, FD-massspectrometry:369.
Embodiment 5: the synthesis of compound 2,4,6-bis-(Three methyl Benzene imido grpup) ethylpyridine
In the there-necked flask of 250 milliliters, nitrogen adds the DAP of 1.63 grams, the Virahol of 80 milliliters and 0.3 milliliter of Glacial acetic acid after blowing row, stirred at ambient temperature is even.Slowly be added dropwise to the 2.72 grams of 2，4，6-trimethyl aniline be dissolved in 20 milliliters of aqueous isopropanols under room temperature, add rear stirring reaction after 2 hours temperature rising reflux react 48 hours.Reaction soln, through concentrating under reduced pressure, obtains 2.70 grams of (productive rate 68%) products after column chromatography for separation.
1h-NMR (δ, ppm, TMS, CDCl3): 8.34 ~ 8.45 (2H, m, ArH), 7.88 (1H, m, ArH), 7.02 ~ 7.24 (4H, m, ArH), 2.32 ~ 2.41 (12H, m, CH
3), 2.21 ~ 2.27 (6H, s, CH
3), 2.02 ~ 2.06 (6H, s, CH
3); Mass spectrum, FD-massspectrometry:397.
Embodiment 6: the synthesis of compound 2,4,6-bis-(2-naphthalene imido grpup) ethylpyridine
In the there-necked flask of 250 milliliters, nitrogen adds the DAP of 1.63 grams, the Virahol of 80 milliliters and 0.3 milliliter of Glacial acetic acid after blowing row, stirred at ambient temperature is even.Slowly be added dropwise to the 2.88 grams of 2-naphthylamines be dissolved in 20 milliliters of aqueous isopropanols under room temperature, add rear stirring reaction after 2 hours temperature rising reflux react 72 hours.Reaction soln, through concentrating under reduced pressure, obtains 2.70 grams of (productive rate 68%) products after column chromatography for separation.
1h-NMR (δ, ppm, TMS, CDCl
3): 8.14 ~ 8.35 (3H, m, ArH), 7.88 ~ 7.74 (8H, m, ArH), 7.18 ~ 7.22 (6H, m, ArH), 2.20 ~ 2.25 (6H, s, CH
3); Mass spectrum, FD-massspectrometry:413.
Embodiment 7: the synthesis of compound 2,6-bis-(benzyl imido grpup) ethylpyridine
In the there-necked flask of 250 milliliters, nitrogen adds the DAP of 1.63 grams, the Virahol of 80 milliliters and 0.22 gram of tosic acid after blowing row, stirred at ambient temperature is even.Slowly be added dropwise to the 2.50 grams of benzyl amine be dissolved in 20 milliliters of aqueous isopropanols under room temperature, add rear stirring reaction after 2 hours temperature rising reflux react 68 hours.Reaction soln, through concentrating under reduced pressure, obtains 2.38 grams of (productive rate 70%) products after column chromatography for separation.
1h-NMR (δ, ppm, TMS, CDCl
3): 8.24 ~ 8.38 (2H, m, ArH), 7.82 ~ 7.95 (3H, m, ArH), 7.08 ~ 7.22 (8H, m, ArH), 2.56 ~ 2.62 (4H, s, CH
2), 2.20 ~ 2.28 (6H, s, CH
3); Mass spectrum, FD-massspectrometry:341.
Embodiment 8: the synthesis of compound 2,6-bis-(8-quinoline imido grpup) ethylpyridine
In the there-necked flask of 250 milliliters, nitrogen adds the DAP of 1.63 grams, the Virahol of 70 milliliters and 0.22 gram of tosic acid after blowing row, stirred at ambient temperature is even.Slowly be added dropwise to the 2.92 grams of 8-quinolylamines be dissolved in 35 milliliters of aqueous isopropanols under room temperature, add rear stirring reaction after 2 hours temperature rising reflux react 72 hours.Reaction soln, through concentrating under reduced pressure, obtains 2.66 grams of (productive rate 64%) products after column chromatography for separation.
1h-NMR (δ, ppm, TMS, CDCl3): 8.36 ~ 8.58 (4H, m, ArH), 7.82 ~ 7.95 (3H, m, ArH), 7.08 ~ 7.22 (8H, m, ArH), 2.20 ~ 2.28 (6H, s, CH
3); Mass spectrum, FD-massspectrometry:415.
(2) preparation of ingredient of solid catalyst
Embodiment 9
In the reactor of fully replacing through high pure nitrogen, add magnesium chloride 4.8g successively, toluene 95mL, epoxy chloropropane 4ml, tributyl phosphate (TBP) 12.5mL, be warming up to 50 DEG C under stirring, and maintain 2.5 hours, after solid dissolves completely, add Tetra hydro Phthalic anhydride 1.4g, continue maintenance 1 hour, solution is cooled to less than-25 DEG C, in 1 hour, drips TiCl
4, slowly be warming up to 80 DEG C, gradually solids is separated out, add 2, the compound 2 of 4-bis-benzoyloxy pentane (0.003 mole) and described structure, 6-bis-(2, 6-di-isopropyl phenyl imido) ethylpyridine (0.003 mole), holding temperature 1 hour, after heat filtering, add toluene 150mL, washing secondary, obtain solid, add toluene 100mL, stir 30 minutes, be warmed up to 110 DEG C, carry out three washings, time is respectively 10 minutes, add hexane 60mL again to wash twice, obtain solids 7.9g (solid ingredient), containing Ti:3.6%, Mg:25.4%, Cl:50.1%.
Embodiment 10
Identical with embodiment 9, only compound 2,6-bis-(2, the 6-di-isopropyl phenyl imido) ethylpyridine in embodiment is replaced with 2,6-bis-(2,6-imino dimethyl benzene) ethylpyridine.
Embodiment 11
Identical with embodiment 9, only compound 2,6-bis-(2, the 6-di-isopropyl phenyl imido) ethylpyridine in embodiment is replaced with 2,6-bis-(2,4,6-Three methyl Benzene imido grpup) ethylpyridine.
Embodiment 12
Identical with embodiment 9, only compound 2,6-bis-(2, the 6-di-isopropyl phenyl imido) ethylpyridine in embodiment is replaced with 2,6-bis-(8-quinoline imido grpup) ethylpyridine.
Embodiment 13
Identical with embodiment 9, only compound 2,6-bis-(2, the 6-di-isopropyl phenyl imido) ethylpyridine in embodiment is replaced with 2,6-bis-(2-naphthalene imido grpup) ethylpyridine.
Embodiment 14
Identical with embodiment 9, only compound 2, the 4-bis-benzoyloxy pentane in embodiment is replaced with 3-ethyl-2,4-bis-benzoyloxy pentane.
Embodiment 15
In the reactor of fully replacing through high pure nitrogen, add magnesium chloride 4.8g successively, toluene 95mL, epoxy chloropropane 4ml, tributyl phosphate (TBP) 12.5mL, be warming up to 50 DEG C under stirring, and maintain 2.5 hours, after solid dissolves completely, add Tetra hydro Phthalic anhydride 1.4g, continue maintenance 1 hour, solution is cooled to less than-25 DEG C, in 1 hour, drips TiCl
4, be slowly warming up to 80 DEG C, gradually solids separated out, add 2,4-bis-benzoyloxy pentane (0.006 mole) holding temperature 1 hour, after heat filtering, add toluene 150mL, washing secondary, obtains solid, adds toluene 100mL, stir 30 minutes, be warmed up to 110 DEG C, carry out three washings, the time is respectively 10 minutes.Add the compound 2 of hexane 60mL and described structure again, 6-bis-(2,6-di-isopropyl phenyl imido) ethylpyridine (0.006 mole), stir 30 minutes, add hexane 60mL to wash twice, obtain solids 7.9g (solid ingredient), containing Ti:3.8%, Mg:20.2%, Cl:51.8%.
(3) catalyzing propone polymerization experiment
Embodiment 16
Volume is the stainless steel cauldron of 5L, after gaseous propylene is fully replaced, adds AlEt
32.5mL, Cyclohexylmethyldimethoxysilane (CHMMS) 5ml makes Al/Si (mol)=25, add solid ingredient 10mg and the 1.2NL hydrogen of above-described embodiment 9 preparation again, pass into liquid propene 2.5L, be warming up to 70 DEG C, maintain this temperature 1 hour, cooling, bleed off pressure, discharging obtains PP resin, active 50600g/gCat, the degree of isotacticity 97.8% (subordinate list 1) of resulting polymers.
Embodiment 17
With embodiment 16, just by the solid ingredient in the solid ingredient alternative embodiment 9 in above-described embodiment 10, the results are shown in subordinate list 1.
Embodiment 18
With embodiment 16, just by the solid ingredient in the solid ingredient alternative embodiment 9 in above-described embodiment 11, the results are shown in subordinate list 1.
Embodiment 19
With embodiment 16, just by the solid ingredient in the solid ingredient alternative embodiment 9 in above-described embodiment 12.The results are shown in subordinate list 1.
Embodiment 20
With embodiment 16, just by the solid ingredient in the solid ingredient alternative embodiment 9 in above-described embodiment 13, the results are shown in subordinate list 1.
Embodiment 21
With embodiment 16, just by the solid ingredient in solid ingredient alternative embodiment 9 synthesized in above-described embodiment 14, the results are shown in subordinate list 1.
Embodiment 22
With embodiment 16, just by the solid ingredient in solid ingredient alternative embodiment 9 synthesized in above-described embodiment 15, the results are shown in subordinate list 1.
Embodiment 23
With embodiment 16, just the polymerization reaction time in embodiment is extended for 2 hours, the results are shown in subordinate list 1.
Embodiment 24
With embodiment 16, just the polymerization reaction time in embodiment is extended for 3 hours, the results are shown in subordinate list 1.
Embodiment 25
With embodiment 20, just the polymerization reaction time in embodiment is extended for 2 hours, the results are shown in subordinate list 1.
Embodiment 26
With embodiment 20, just the polymerization reaction time in embodiment is extended for 3 hours, the results are shown in subordinate list 1.
Embodiment 27
With embodiment 17, be just 7.2NL by the hydrogenation quantitative change in embodiment, concrete outcome sees attached list 1.
Comparative example 1
The synthesis of catalyst component: in the reactor of fully replacing through high pure nitrogen, add magnesium chloride 4.8g successively, toluene 95mL, epoxy chloropropane 4ml, tributyl phosphate (TBP) 12.5mL, be warming up to 50 DEG C under stirring, and maintain 2.5 hours, after solid dissolves completely, add Tetra hydro Phthalic anhydride 1.4g, continue maintenance 1 hour, solution is cooled to less than-25 DEG C, in 1 hour, drips TiCl
4, be slowly warming up to 80 DEG C, gradually solids separated out, add 2,4-bis-benzoyloxy pentane (0.003 mole), holding temperature 1 hour, after heat filtering, add toluene 150mL, washing secondary, obtain solid, add toluene 100mL, be warmed up to 110 DEG C, carry out three washings, the time is respectively 10 minutes, hexane 60mL, stir 30 minutes, then add hexane 60mL and wash three times.Obtain solids 7.4g (solid ingredient), containing Ti:2.4%, Mg:22.0%, Cl:50.6%.
Propylene polymerization is tested: volume is the stainless steel cauldron of 5L, after gaseous propylene is fully replaced, adds AlEt
32.5mL, Cyclohexylmethyldimethoxysilane (CHMMS) 5ml makes Al/Si (mol)=25, add solid ingredient 10mg and the 1.2NL hydrogen of above-mentioned preparation again, pass into liquid propene 2.5L, be warming up to 70 DEG C, maintain this temperature 1 hour, cooling, bleed off pressure, discharging obtains PP resin, the results are shown in subordinate list 1.
Comparative example 2
With comparative example 1, be just 7.2NL by the hydrogenation quantitative change in comparative example 1, concrete outcome sees attached list 1.
Table 1
For compound shown in general formula I and general formula I I is as compound internal electron donor in embodiment 16, and in comparative example 1, only use compound shown in general formula I I to be internal electron donor, the preparation of other catalyst component is identical with propylene polymerization condition, as seen from Table 1, in embodiment, corresponding catalyzer has higher activity and orientation property, and the isotactic index of resulting polymers is high, molecular weight distribution is wider.In addition, compared with the catalyzer in comparative example, gained catalyst activity decay of the present invention is comparatively slow, and hydrogen response can be better.
Claims (7)
1. for the catalyst component of propylene polymerization, it is characterized in that, containing magnesium, titanium, halogen and internal electron donor in described catalyst component, and the compound internal electron donor that described internal electron donor is compound shown in general formula I and dibasic alcohol ester compound, shown in general formula I, compound structure is as follows
In general formula I, R and R ' is identical or different, for containing substituting group or not containing substituent C
1~ C
20alkyl, C
2~ C
20thiazolinyl or C
6~ C
20containing or not containing heteroatomic aryl, and described substituting group is selected from alkyl, hydroxyl and halogen, described heteroatoms is N;
R
1~ R
5identical or different, be hydrogen, halogen atom, hydroxyl, alkoxyl group or containing substituting group or not containing substituent C
1~ C
12alkyl, C
2~ C
12thiazolinyl or C
6~ C
20aryl;
X is carbon or nitrogen.
2. catalyst component according to claim 1, is characterized in that, described dibasic alcohol ester compound is such as compound shown in general formula I I,
In general formula I I, R
1and R
2identical or different, for the C of halogen substiuted or unsubstituted straight chain, side chain or ring-type
1~ C
20alkyl; R
3~ R
6identical or different, be hydrogen, halogen atom, hydroxyl, alkoxyl group or containing substituting group or not containing substituent C
1~ C
12alkyl, C
2~ C
12thiazolinyl or C
6~ C
20aryl, and R
3~ R
6between two or more groups can connect into ring; R
iand R
iIidentical or different, be the C of hydrogen or straight chain, side chain or ring-type
1~ C
20alkyl, R
iand R
iIbetween can connect into ring; N is the integer of 0 ~ 10.
3. catalyst component according to claim 2, is characterized in that, described dibasic alcohol ester compound is selected from 2-sec.-propyl-1,3-bis-benzoyloxy propane, 2-butyl-1,3-bis-benzoyloxy propane, 2-cyclohexyl-1,3-bis-benzoyloxy propane, 2-benzyl-1,3-bis-benzoyloxy propane, 2-phenyl-1,3-bis-benzoyloxy propane, 2-(1-naphthyl)-1,3-bis-benzoyloxy propane, 2-sec.-propyl-1,3-diethyl carboxyl propane, 2-sec.-propyl-2-isopentyl-1,3-bis-benzoyloxy propane, 2-sec.-propyl-2-isobutyl--1,3-bis-benzoyloxy propane, 2-sec.-propyl-2-isopentyl-1,3-dipropyl carboxyl propane, 2-sec.-propyl-2-butyl-1,3-bis-benzoyloxy propane, 2-sec.-propyl-2-isopentyl-1-benzoyloxy-3-fourth carboxyl propane, 2-sec.-propyl-2-isopentyl-1-benzoyloxy-3-Chinese cassia tree carboxyl propane, 2-sec.-propyl-2-isopentyl-1-benzoyloxy-3-second carboxyl propane, 2,2-bicyclopentyl-1,3-bis-benzoyloxy propane, 2,2-dicyclohexyl-1,3-bis-benzoyloxy propane, 2,2-dibutyl-1,3-bis-benzoyloxy propane, 2,2-diisobutyl-1,3-bis-benzoyloxy propane, 2,2-di-isopropyl-1,3-bis-benzoyloxy propane, 2,2-diethyl-1,3-bis-benzoyloxy propane, 2-ethyl-2-butyl-1,3-bis-benzoyloxy propane, 2,4-bis-benzoyloxy pentane, 3-ethyl-2,4-bis-benzoyloxy pentane, 3-methyl-2,4-bis-benzoyloxy pentane, 3-propyl group-2,4-bis-benzoyloxy pentane, 3-sec.-propyl-2,4-bis-benzoyloxy pentane, 2,4-bis-(2-propylbenzene carboxyphenyl) pentane, 2,4-bis-(4-propylbenzene carboxyphenyl) pentane, 2,4-bis-(2,4-dimethyl benzene carboxyphenyl) pentane, 2,4-bis-(2,4 dichloro benzene carboxyphenyl) pentane, 2,4-bis-(4-chlorobenzene carboxyphenyl) pentane, 2,4-bis-(4-isopropyl benzene carboxyphenyl) pentane, 2,4-bis-(4-butylbenzene carboxyphenyl) pentane, 2,4-bis-(4-isobutyl-benzene carboxyphenyl) pentane, 3,5-bis-benzoyloxy heptane, 4-ethyl-3,5-bis-benzoyloxy heptane, 4-propyl group-3,5-bis-benzoyloxy heptane, 4-sec.-propyl-3,5-bis-benzoyloxy heptane, 3,5-bis-(4-propylbenzene carboxyphenyl) heptane, 3,5-bis-(4-isopropyl benzene carboxyphenyl) heptane, 3,5-bis-(4-isobutyl-benzene carboxyphenyl) heptane, 3,5-bis-(4-butylbenzene carboxyphenyl) heptane, 2-benzoyloxy-4-(4-isobutyl-benzene carboxyphenyl) pentane, 2-benzoyloxy-4-(4-butylbenzene carboxyphenyl) pentane, 2-benzoyloxy-4-(4-propylbenzene carboxyphenyl) pentane, 3-benzoyloxy-5-(4-isobutyl-benzene carboxyphenyl) heptane, 3-benzoyloxy-5-(4-butylbenzene carboxyphenyl) heptane, 3-benzoyloxy-5-(4-propylbenzene carboxyphenyl) heptane, 9,9-bis-benzoyloxy methyl fluorenes, 9,9-dipropyl carboxymethyl group fluorenes, 9,9-bis-isobutyl carboxymethyl group fluorenes, 9,9-bis-fourth carboxymethyl group fluorenes, 9,9-bis-benzoyloxy methyl-4-tertiary butyl fluorenes, 9,9-bis-benzoyloxy methyl-4-propyl group fluorenes, 9,9-bis-benzoyloxy methyl isophthalic acid, 2,3,4-tetrahydrochysene fluorenes, 9,9-bis-benzoyloxy methyl isophthalic acid, 2,3,4,5,6,7,8-octahydro fluorenes, 9,9-bis-benzoyloxy methyl-2,3,6,7-bis-phenylpropyl alcohol indenes, 9,9-bis-benzoyloxy methyl isophthalic acid, 8-dichloro fluorenes, 7,7-bis-benzoyloxy methyl-2,5-norbornadiene, Isosorbide-5-Nitrae-two benzoyloxy butane, 2,3-di-isopropyl-Isosorbide-5-Nitrae-two benzoyloxy butane, 2,3-dibutyl-Isosorbide-5-Nitrae-two benzoyloxy butane, 1,2-bis-benzoyloxy benzene, 3-ethyl-1,2-bis-benzoyloxy benzene, 4-butyl-1,2-bis-benzoyloxy benzene, 1,8-bis-benzoyloxy naphthalene, 2-ethyl-1,8-bis-benzoyloxy naphthalene, 2-propyl group-1,8-bis-benzoyloxy naphthalene, 2-butyl-1,8-bis-benzoyloxy naphthalene, 4-butyl-1,8-bis-benzoyloxy naphthalene, 4-isobutyl--1,8-bis-benzoyloxy naphthalene, 4-sec.-propyl-1,8-bis-benzoyloxy naphthalene, one or more in 4-propyl group-1,8-bis-benzoyloxy naphthalene.
4. catalyst component according to claim 1, is characterized in that, is selected from pyridyl, pyrryl, pyrimidyl and quinolyl described in R and R ' containing heteroatomic aryl.
5. catalyst component according to claim 1, is characterized in that, compound shown in described general formula I is selected from 2,6-bis-(2,6-imino dimethyl benzene) ethylpyridine, 2,6-bis-(2,6-di-isopropyl phenyl imido) ethylpyridine, 2,6-bis-(phenyl imido) ethylpyridine, 2,6-bis-(2-naphthalene imido grpup) ethylpyridine, 2,6-bis-(1-naphthalene imido grpup) ethylpyridine, 2,6-bis-(fourth imido grpup) ethylpyridine, 2,6-bis-(own imido grpup) ethylpyridine, 2,6-bis-(penta imido grpup) ethylpyridine, 2,6-bis-(pungent imido grpup) ethylpyridine, 2,6-bis-(benzyl imido grpup) ethylpyridine, 2,6-bis-(4-chlorobenzene imido grpup) ethylpyridine, 2,6-bis-(4-trifluoromethyl phenyl imido) ethylpyridine, 2,6-bis-(2-trifluoromethyl phenyl imido) ethylpyridine, 2,6-bis-(2-chloro-6-hydroxybenzene imido grpup) ethylpyridine, 2,6-bis-(8-quinoline imido grpup) ethylpyridine, 2,6-bis-(4-quinoline imido grpup) ethylpyridine, 2,6-bis-(3-quinoline imido grpup) ethylpyridine, 2,6-bis-(2,4,6-Three methyl Benzene imido grpup) ethylpyridine, 2-(phenyl imido) ethyl-6-(2,6-imino dimethyl benzene) ethylpyridine, 2-(phenyl imido) ethyl-6-(2,6-di-isopropyl phenyl imido) ethylpyridine, 2-(phenyl imido) ethyl-6-(to chlorobenzene imido grpup) ethylpyridine, 2-(2,6-di-isopropyl phenyl imido) ethyl-6-(2,6-imino dimethyl benzene) ethylpyridine, 2-(to chlorobenzene imido grpup) ethyl-6-(2,6-di-isopropyl phenyl imido) ethylpyridine, 2-(2-hydroxyl-4-chlorobenzene imido grpup) ethyl-6-(to chlorobenzene imido grpup) ethylpyridine, 2,6-bis-(2-hydroxybenzene imido grpup) ethylpyridine, 2,6-bis-(2-ethylbenzene imido grpup) ethylpyridine, 2,6-bis-(4-ethylbenzene imido grpup) ethylpyridine, 2,6-bis-(2-propylbenzene imido grpup) ethylpyridine, 2,6-bis-(4-propylbenzene imido grpup) ethylpyridine, 2,6-bis-(2-butylbenzene imido grpup) ethylpyridine, 2,6-bis-(4-butylbenzene imido grpup) ethylpyridine, 2,6-bis-(2,6-imino dimethyl benzene) ethylbenzene, one or more in 2,6-bis-(2,6-di-isopropyl phenyl imido) ethylbenzene.
6. according to the catalyst component in Claims 1 to 5 described in any one, it is characterized in that, the weight percentage of compound shown in general formula I in described catalyst component is 0.01 ~ 20%, be preferably 1 ~ 15%, be more preferably 2 ~ 10%; The weight percentage of described dibasic alcohol ester compound in described catalyst component is 0.01 ~ 20%, is preferably 1 ~ 15%.
7. a catalyzer, comprises component a as described below and b, and selectable amount of component b, wherein:
A: the catalyst component as above in claim 1 ~ 6 described in any one, b: promotor organo-aluminium compound, c: external electron donor silicoorganic compound.
Priority Applications (11)
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| CN201410168507.8A CN105085746B (en) | 2014-04-24 | 2014-04-24 | Catalytic component and its catalyst for propylene polymerization |
| MYPI2016703904A MY176619A (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization, and catalyst containing the same |
| US15/306,255 US10208145B2 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization, and catalyst containing the same |
| CA2946777A CA2946777C (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization, and catalyst containing the same |
| EP15782847.6A EP3135697B1 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization and catalyst thereof |
| SG11201608921YA SG11201608921YA (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization and catalyst containing the same |
| PCT/CN2015/077381 WO2015161827A1 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization and catalyst thereof |
| KR1020167032804A KR102293704B1 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization and catalyst thereof |
| RU2016145949A RU2688689C2 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerisation and catalyst containing it |
| JP2016564188A JP6804302B2 (en) | 2014-04-24 | 2015-04-24 | Catalyst components for olefin polymerization and catalysts containing them |
| SA516380135A SA516380135B1 (en) | 2014-04-24 | 2016-10-24 | Catalyst Component for Olefin Polymerization, and Catalyst Containing the Same |
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