CN105085749B - Catalytic component and its catalyst for propylene polymerization - Google Patents
Catalytic component and its catalyst for propylene polymerization Download PDFInfo
- Publication number
- CN105085749B CN105085749B CN201410169052.1A CN201410169052A CN105085749B CN 105085749 B CN105085749 B CN 105085749B CN 201410169052 A CN201410169052 A CN 201410169052A CN 105085749 B CN105085749 B CN 105085749B
- Authority
- CN
- China
- Prior art keywords
- ethylpyridine
- bis
- imido
- catalytic component
- butyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention provides a kind of catalytic component for propylene polymerization, contain magnesium, titanium, halogen and internal electron donor in the catalytic component, and the internal electron donor is the compound internal electron donor of compound shown in formula I and dibasic acid ester, compound structure shown in formula I is as follows, in formula I, R and R ' are identical or different, for the C containing substituent or without substituent1~C20Alkyl, C2~C20Alkenyl or C6~C20Contain or not contain heteroatomic aryl, and the substituent is selected from alkyl, hydroxyl and halogen, and the hetero atom is N；R1~R5It is identical or different, it is hydrogen, halogen atom, hydroxyl, alkoxy or the C containing substituent or without substituent1~C12Alkyl, C2~C12Alkenyl or C6~C20Aryl；X is carbon or nitrogen.The present invention correspondingly provides a kind of catalyst.Gained catalyst of the invention has higher activity and capacity of orientation, and the molecular weight distribution of resulting polymers is wider.
Description
Technical field
The present invention relates to propylene polymerization field, and in particular to a kind of Ziegler-Natta catalyst for propylene polymerization
Component and its catalyst.
Background technology
Ziegler-Natta catalyst is catalyst the most frequently used in propylene polymerization.For traditional propylene polymerization
For Ziegler-Natta catalyst, with the development of the electron donor compound in catalyst, catalyst is also continuously updated
Regenerate.TiCl of the research and development of catalyst from the first generation3AlCl3/AlEt2The TiCl of Cl systems and the second generation3/AlEt2Cl systems, are arrived
The magnesium chloride of the third generation is the TiCl that carrier, monoesters or aromatic dibasic acid ester are internal electron donor, silane is external electron donor4·
ED·MgCl2/AlR3ED systems, the catalytic polymerization activity and gained polypropylene isotacticity Gao Douyou of catalyst are very
Big raising, and the catalyst system that two ethers newly developed, two esters are internal electron donor.In the prior art, it is used for
The titanium catalyst system of propylene polymerization is more using magnesium, titanium, halogen and electron donor as basis, wherein electron donor compound
It is one of component essential in catalytic component.At present, it has been disclosed that a variety of electron donor compounds, such as monocarboxylic esters
Or multi-carboxylate, acid anhydrides, ketone, monoether or polyether, alcohol, amine etc. and its derivative, wherein more conventional is fragrant binary carboxylic
Esters of gallic acid, such as n-butyl phthalate or diisobutyl phthalate etc., reference can be made to United States Patent (USP) US4784983.
In United States Patent (USP) US4971937 and the component for olefin polymerization catalyst disclosed in European patent EP 0728769, adopt
It is electron donor with special 1, the 3- diether compounds containing two ether groups, such as 2- isopropyl -2- isopentyl -1,3-
Dimethoxy propane, 2,2- diisobutyls -1,3- dimethoxy propane and 9,9- bis- (methoxyl methyl) fluorenes etc..Thereafter disclose again
A kind of special dibasic aliphatic carboxylic acid ester compound, such as succinate, malonate, glutarate are (referring to WO98/
56830th, WO98/56834, WO01/57099, WO01/63231 and WO00/55215), the use of this kind of electron donor compound
The activity of catalyst can be not only improved, and the molecular weight distribution of gained acrylic polymers is substantially widened.
But this area still needs to be made improvements to Ziegler-Natta catalyst and its catalytic component, to cause it
With higher catalyst activity and capacity of orientation, and make it that the molecular weight distribution of resulting polymers is wider.
The content of the invention
It is an object of the invention to develop a kind of catalyst and its component for propylene polymerization.Inventor has found, passes through
Increase a kind of compound as shown in formula I on the basis of existing internal electron donor to urge for compound internal electron donor composition is new
When changing polymerization reaction system, gained catalyst has higher activity and capacity of orientation, and the molecular weight distribution of resulting polymers
It is wider.
Therefore, the present invention provides a kind of catalytic component for propylene polymerization, contain in the catalytic component magnesium,
Titanium, halogen and internal electron donor, and the internal electron donor is the compound interior electron of compound shown in formula I and dibasic acid ester
Body, compound structure shown in formula I is as follows,
In formula I, R and R ' are identical or different, for the C containing substituent or without substituent1~C20Alkyl, C2~C20
Alkenyl or C6~C20Contain or not contain heteroatomic aryl, and the substituent is selected from alkyl, hydroxyl and halogen, described
Hetero atom is N；
R1~R5It is identical or different, it is hydrogen, halogen atom, hydroxyl, alkoxy or the C containing substituent or without substituent1~
C12Alkyl, C2~C12Alkenyl or C6~C20Aryl；
X is carbon or nitrogen.
It is preferred that dibasic acid ester of the present invention is the compound as shown in formula II,
In formula II, R and R ' are identical or different, for the straight chain containing substituent or without substituent, side chain or ring-type
C1~C20Alkyl, and the substituent is selected from hydroxyl and halogen；R1~R4It is identical or different, it is hydrogen, halogen atom, hydroxyl, alkane
Epoxide or the C containing substituent or without substituent1~C12Alkyl, C2~C12Alkenyl or C6~C20Aryl.
In a kind of specific embodiment, the dibasic acid ester is selected from diethyl phthalate, phthalic acid two
Propyl ester, diisobutyl phthalate, n-butyl phthalate, amyl phthalate, phthalic acid two are different
Pentyl ester, the peopentyl ester of phthalic acid two, DHP, dibutyl phthalate (DHP), dioctyl phthalate, neighbour
The nonyl ester of phthalic acid two, 2- methylphthalic acids diisobutyl ester, 2- methylphthalic acids di-n-butyl, 2- propyl group neighbours benzene two
Diisobutyl formate, 2- propyl group n-butyl phthalate, 2- butyl diisobutyl phthalate, 2- butyl O-phthalics
Sour di-n-butyl, 2- propyl group diisobutyl phthalate, 2- propyl group n-butyl phthalate, 4- propyl group phthalic acids
Diisobutyl ester, 4- butyl n-butyl phthalate, 2- chloro-o-phthalic acids diisobutyl ester, two positive fourth of 2- chloro-o-phthalic acids
In ester, 4- chloro-o-phthalic acids diisobutyl ester, 4- chloro-o-phthalic acids di-n-butyl, 4- methoxyl group n-butyl phthalates
One or more.
In another particular embodiment of the invention, the dibasic acid ester is fatty group dibasic acid.Preferably, the binary
Acid esters is dimethyl malenate, diethyl malonate, 2- diethyl isopropyls, 2- normal-butyl -2- isobutyl propylmalonic acids
Diethylester, 2- diethyl butylmalonates, 2- iso-butyl diethyl malonates, 2,2- diisobutyls diethyl malonate, 2-
Isoamyl-malonic acid diethylester, dipropyl malonate, dibutyl malonate, dimethyl succinate, diethyl succinate, 2,3- bis-
Isopropyl diethyl succinate, 2,3- diisobutyls diethyl succinate, 2,3- di-n-butyls diethyl succinate, succinic acid two
Propyl ester, dipropyl succinate, dibutyl succinate, dimethyl glutarate, ethyl glutarate, 3- propyl group ethyl glutarate,
Glutaric acid dipropyl, dibutyl glutarate, dimethyl adipate, diethylene adipate, dipropyl adipate, the fourth of adipic acid two
Ester, dimethyl sebacate, diethyl sebacate, dipropyl sebacate, dibutyl sebacate.
In the present invention, pyridine radicals, pyrrole radicals, pyrimidine are selected from containing heteroatomic aryl described in preferred formula I R and R '
Base and quinolyl.
In a kind of specific embodiment of the present invention, compound shown in formula I is selected from 2,6- bis-, and (2,6- dimethyl benzenes are sub-
Amido) ethylpyridine, 2,6- bis- (2,6- diisopropyls phenyl imido) ethylpyridine, 2,6- bis- (phenyl imido) ethylpyridine,
2,6- bis- (2- naphthalenes imido grpup) ethylpyridine, 2,6- bis- (1- naphthalenes imido grpup) ethylpyridine, 2,6- bis- (fourth imido grpup) ethyl pyrrole
Pyridine, 2,6- bis- (own imido grpup) ethylpyridine, 2,6- bis- (penta imido grpup) ethylpyridine, 2,6- bis- (pungent imido grpup) ethyl pyrrole
Pyridine, 2,6- bis- (benzyl imido grpup) ethylpyridine, 2,6- bis- (4- chlorobenzenes imido grpup) ethylpyridine, (the 4- trifluoromethylbenzenes of 2,6- bis-
Imido grpup) ethylpyridine, 2,6- bis- (2- trifluoromethyls phenyl imido) ethylpyridine, (the chloro- 6- hydroxy benzenes imines of 2- of 2,6- bis-
Base) 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- trimethylbenzenes imido grpup) ethylpyridine, 2- (phenyl imido) ethyl-
6- (2,6- imino dimethyl benzenes) ethylpyridine, 2- (phenyl imido) ethyls -6- (2,6- diisopropyls phenyl imido) ethyl
Pyridine, 2- (phenyl imido) ethyls -6- (to chlorobenzene imido grpup) ethylpyridine, 2- (2,6- diisopropyls phenyl imido) ethyl -
6- (2,6- imino dimethyl benzenes) ethylpyridine, 2- (to chlorobenzene imido grpup) ethyl -6- (2,6- diisopropyls phenyl imido)
Ethylpyridine, 2- (2- hydroxyl -4- chlorobenzenes imido grpup) ethyl -6- (to chlorobenzene imido grpup) ethylpyridine, (the 2- hydroxy benzenes of 2,6- bis-
Imido grpup) ethylpyridine, 2,6- bis- (2- ethyls phenyl imido) ethylpyridine, 2,6- bis- (4- ethyls phenyl imido) ethyl pyrrole
Pyridine, 2,6- bis- (2- propyl group phenyl imido) ethylpyridine, 2,6- bis- (4- propyl group phenyl imido) ethylpyridine, (the 2- fourths of 2,6- bis-
Base phenyl imido) ethylpyridine, 2,6- bis- (4- butyl phenyl imido) ethylpyridine, 2,6- bis- (2,6- imino dimethyl benzenes)
One or more in ethylo benzene, 2,6- bis- (2,6- diisopropyls phenyl imido) ethylo benzene.
In the present invention, in a kind of embodiment, weight of the compound in the catalytic component shown in formula I
Percentage composition is 0.01~20%, preferably 1~15%, more preferably 2~10%；The dibasic acid ester is in the catalyst group
Weight percentage in point is 0.01~20%, preferably 1~15%.
The present invention also provides a kind of catalyst, including component a and b as described below, and selectable component c, wherein：
a：Catalytic component as described above,
b：Co-catalyst organo-aluminum compound,
c：External electron donor organo-silicon compound.
Above-mentioned catalyst component can use following methods to prepare：
Method 1：Magnesium halide is dissolved in the homogeneous solution that organic epoxy compound thing and organic phosphorus compound form, can also be added
Enter inert diluent.Above-mentioned homogeneous solution and titanium tetrahalide or derivatives thereof mix, and when thering is precipitation additive to deposit in reaction system
When, just have solids precipitation.The formula I and compounds of formula II are attached on solids, then with titanium tetrahalide or
Inert diluent processing, then uses described compound of Formula I to handle, obtains including the compositions such as titanium, magnesium, halogen, electron donor
Solid catalyst.
Method 2：By magnesium halide or organo-magnesium compound, alcohol compound and titanate ester or halogenated titanium compound in inertia
Stirring is sufficiently mixed in solvent, is cooled down after heating and obtains ball-type carrier alkoxyl magnesium or alkoxy-magnesium chloride or addition atent solvent
Obtain uniform alcohol adduct solution.Above-mentioned carrier or homogeneous solution and titanium tetrahalide or derivatives thereof are mixed, maintained under low temperature
Heat temperature raising after a period of time, the compound of the formula I and II is added, is then handled with titanium tetrahalide or inert diluent,
Finally the solid catalyst for including the compositions such as titanium, magnesium, halogen, electron donor is obtained by filtering, wash, after drying.
Method 3：Magnesium halide is dissolved in the homogeneous solution that organic epoxy compound thing and organic phosphorus compound form, can also be added
Enter inert diluent, add the compound of the formula I and II.Above-mentioned solution and titanium tetrahalide or derivatives thereof are mixed, it is low
Temperature is lower to maintain heat temperature raising after a period of time, then is handled with titanium tetrahalide or inert diluent, last filtered, washing, dries
The solid catalyst for including the compositions such as titanium, magnesium, halogen, electron donor is obtained afterwards.
Method 4：Magnesium halide is dissolved in the homogeneous solution that organic epoxy compound thing and organic phosphorus compound form, can also be added
Enter inert diluent.Above-mentioned homogeneous solution and titanium tetrahalide or derivatives thereof mix, and when thering is precipitation additive to deposit in reaction system
When, just have solids precipitation.The compounds of formula II is attached on solids, uses institute again after titanium tetrahalide is handled
The compound of Formula I processing stated, is then handled with inert diluent, finally obtain including after filtration, washing and drying titanium, magnesium,
The solid catalyst of the compositions such as halogen, electron donor.
When catalyst of the present invention is used to be catalyzed propylene polymerization, catalyst activity is high, the isotactic of resulting polymers
Index 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 formula I
Embodiment 1：The synthesis of compound 2,6- bis- (phenyl imido) ethylpyridine
In one 250 milliliters of there-necked flask, nitrogen blow row after add 1.63 grams DAP, 80 milliliters
Isopropanol and 0.2 milliliter of glacial acetic acid, stir at room temperature.It is slowly added dropwise at room temperature molten into 20 milliliters of isopropanols are dissolved in
1.86 grams of aniline in liquid, adding rear stirring reaction, after 2 hours temperature rising reflux reaction 48 hours.Reaction solution through being concentrated under reduced pressure,
2.16 grams of (yield 69%) products are obtained after crossing column chromatography for separation.1H-NMR(δ,ppm,TMS,CDCl3):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, CH3)；Mass spectrum, FD-mass
spectrometry:313。
Embodiment 2：The synthesis of compound 2,6- bis- (to chlorobenzene imido grpup) ethylpyridine
In one 250 milliliters of there-necked flask, nitrogen blow row after add 1.63 grams DAP, 80 milliliters
Isopropanol and 0.2 milliliter of glacial acetic acid, stir at room temperature.It is slowly added dropwise at room temperature molten into 20 milliliters of isopropanols are dissolved in
2.44 grams of parachloroanilinum in liquid, adding rear stirring reaction, after 2 hours temperature rising reflux reaction 60 hours.Reaction solution is dense through depressurizing
Contracting, 2.16 grams of (yield 69%) products are obtained after crossing column chromatography for separation.1H-NMR(δ,ppm,TMS,CDCl3):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, CH3)；Mass spectrum, FD-
mass spectrometry:381。
Embodiment 3：The synthesis of compound 2,6- bis- (2,6- diisopropyls phenyl imido) ethylpyridine
In one 250 milliliters of there-necked flask, nitrogen blow row after add 1.63 grams DAP, 80 milliliters
Isopropanol and 0.3 milliliter of glacial acetic acid, stir at room temperature.It is slowly added dropwise at room temperature molten into 20 milliliters of isopropanols are dissolved in
3.56 grams of 2,6-DIPAs in liquid, adding rear stirring reaction, after 2 hours temperature rising reflux reaction 72 hours.Reaction solution
Through being concentrated under reduced pressure, 3.61 grams of (yield 75%) products are obtained 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, CH3), 1.13~1.37 (24H, m, CH3)；Mass spectrum, FD-mass spectrometry:481.Embodiment 4：
The synthesis of compound 2,6- bis- (2,6- imino dimethyl benzenes) ethylpyridine
In one 250 milliliters of there-necked flask, nitrogen blow row after add 1.63 grams DAP, 80 milliliters
Isopropanol and 0.3 milliliter of glacial acetic acid, stir at room temperature.It is slowly added dropwise at room temperature molten into 20 milliliters of isopropanols are dissolved in
2.45 grams of 2,6- dimethylanilines in liquid, adding rear stirring reaction, after 2 hours temperature rising reflux reaction 68 hours.Reaction solution passes through
It is concentrated under reduced pressure, 2.58 grams of (yield 70%) products is obtained after column chromatography for separation.1H-NMR(δ,ppm,TMS,CDCl3):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, CH3),2.01
~2.18 (12H, m, CH3),；Mass spectrum, FD-mass spectrometry:369.
Embodiment 5：The synthesis of compound 2,4,6- bis- (trimethylbenzene imido grpup) ethylpyridine
In one 250 milliliters of there-necked flask, nitrogen blow row after add 1.63 grams DAP, 80 milliliters
Isopropanol and 0.3 milliliter of glacial acetic acid, stir at room temperature.It is slowly added dropwise at room temperature molten into 20 milliliters of isopropanols are dissolved in
2.72 gram 2 in liquid, 4,6- trimethylanilines, adding rear stirring reaction, after 2 hours temperature rising reflux reaction 48 hours.Reaction solution
Through being concentrated under reduced pressure, 2.70 grams of (yield 68%) products are obtained 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, CH3),
2.21~2.27 (6H, s, CH3), 2.02~2.06 (6H, s, CH3)；Mass spectrum, FD-mass spectrometry:397.
Embodiment 6：The synthesis of compound 2,4,6- bis- (2- naphthalenes imido grpup) ethylpyridine
In one 250 milliliters of there-necked flask, nitrogen blow row after add 1.63 grams DAP, 80 milliliters
Isopropanol and 0.3 milliliter of glacial acetic acid, stir at room temperature.It is slowly added dropwise at room temperature molten into 20 milliliters of isopropanols are dissolved in
2.88 grams of 2- naphthylamines in liquid, adding rear stirring reaction, after 2 hours temperature rising reflux reaction 72 hours.Reaction solution is dense through depressurizing
Contracting, obtains 2.70 grams of (yield 68%) products after column chromatography for separation.1H-NMR(δ,ppm,TMS,CDCl3):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, CH3)；Matter
Spectrum, FD-mass spectrometry:413.
Embodiment 7：The synthesis of compound 2,6- bis- (benzyl imido grpup) ethylpyridine
In one 250 milliliters of there-necked flask, nitrogen blow row after add 1.63 grams DAP, 80 milliliters
Isopropanol and 0.22 gram of p-methyl benzenesulfonic acid, stir at room temperature.It is slowly added dropwise at room temperature into being dissolved in 20 milliliters of isopropyls
2.50 grams of benzyl amine in alcoholic solution, adding rear stirring reaction, after 2 hours temperature rising reflux reaction 68 hours.Reaction solution is through decompression
Concentration, obtains 2.38 grams of (yield 70%) products after column chromatography for separation.1H-NMR(δ,ppm,TMS,CDCl3):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, CH2),
2.20~2.28 (6H, s, CH3)；Mass spectrum, FD-mass spectrometry:341.
Embodiment 8：The synthesis of compound 2,6- bis- (8- quinoline imido grpup) ethylpyridine
In one 250 milliliters of there-necked flask, nitrogen blow row after add 1.63 grams DAP, 70 milliliters
Isopropanol and 0.22 gram of p-methyl benzenesulfonic acid, stir at room temperature.It is slowly added dropwise at room temperature into being dissolved in 35 milliliters of isopropyls
2.92 grams of 8- aminoquinolines in alcoholic solution, adding rear stirring reaction, after 2 hours temperature rising reflux reaction 72 hours.Reaction solution passes through
It is concentrated under reduced pressure, 2.66 grams of (yield 64%) products is obtained 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,
CH3)；Mass spectrum, FD-mass spectrometry:415.
(2) preparation of ingredient of solid catalyst
Embodiment 9
In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 4.8g, toluene 95mL, epoxy chloropropionate are sequentially added
Alkane 4ml, tributyl phosphate (TBP) 12.5mL, 50 DEG C are warming up under stirring, and maintained 2.5 hours, after solid is completely dissolved,
Phthalic anhydride 1.4g is added, continues to 1 hour, solution is cooled to less than -25 DEG C, TiCl is added dropwise in 1 hour4, delay
Slowly 80 DEG C are warming up to, gradually separate out solids, add DNBP (0.003 mole of n-butyl phthalate) and the structure
Compound 2,6- bis- (2,6- diisopropyl phenyl imido) ethylpyridine (0.003 mole), maintain temperature 1 hour, heat filtering
Afterwards, toluene 150mL is added, washing is secondary, obtains solid, adds toluene 100mL, stirs 30 minutes, is warming up to 110 DEG C, carries out
Wash three times, the time is respectively 10 minutes, adds hexane 60mL and washes twice, solids 7.9g (solid constituent) is obtained, containing Ti：
3.7%th, Mg：22.8%th, Cl：50.8%.
Embodiment 10
It is same as Example 9, only by the compound 2 in embodiment, 6- bis- (2,6- diisopropyl phenyl imido) ethyl pyrrole
Pyridine replaces with 2,6- bis- (2,6- imino dimethyl benzenes) ethylpyridine.
Embodiment 11
It is same as Example 9, only by the compound 2 in embodiment, 6- bis- (2,6- diisopropyl phenyl imido) ethyl pyrrole
Pyridine replaces with 2,6- bis- (2,4,6- trimethylbenzenes imido grpup) ethylpyridine.
Embodiment 12
It is same as Example 9, only by the compound 2 in embodiment, 6- bis- (2,6- diisopropyl phenyl imido) ethyl pyrrole
Pyridine replaces with 2,6- bis- (8- quinoline imido grpup) ethylpyridine.
Embodiment 13
It is same as Example 9, the compound DNBP in embodiment is only replaced with into DIBP (diisobutyl phthalate).
Embodiment 14
In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 4.8g, toluene 95mL, epoxy chloropropionate are sequentially added
Alkane 4ml, tributyl phosphate (TBP) 12.5mL, 50 DEG C are warming up under stirring, and maintained 2.5 hours, after solid is completely dissolved,
Phthalic anhydride 1.4g is added, continues to 1 hour, solution is cooled to less than -25 DEG C, TiCl is added dropwise in 1 hour4, delay
Slowly 80 DEG C are warming up to, gradually separate out solids, added (0.006 mole) of DNBP and maintain temperature 1 hour, after heat filtering, add
Toluene 150mL, washing is secondary, obtains solid, adds toluene 100mL, stirs 30 minutes, is warming up to 110 DEG C, is washed three times
Wash, the time is respectively 10 minutes.Add the compound 2 of hexane 60mL and the structure, (2, the 6- diisopropyl benzene imines of 6- bis-
Base) ethylpyridine (0.006 mole), stirs 30 minutes, adds hexane 60mL and wash twice, obtain solids 7.9g (solid groups
Point), containing Ti：3.5%th, Mg：24.2%th, Cl：50.6%.
Embodiment 15
In the reactor being sufficiently displaced from by high pure nitrogen, add 300mLTiCl4, -20 DEG C are cooled to, adds magnesium chloride
Alcohol adduct carrier 7.0g (see patent CN1330086A), when being warming up to 40 DEG C under stirring stage by stage, add DNBP (0.003 mole)
And the compound 2 of the structure, 6- bis- (2,6- diisopropyl phenyl imido) ethylpyridine (0.003 mole), maintain temperature 2 small
When, after filtering.Add TiCl4100mL, 110 DEG C are warming up to, is handled three times.Add hexane 60mL washings three times.
To solids 7.1g (solid constituent), containing Ti：3.5%th, Mg：25.2%th, Cl：51.6%.
Embodiment 16
In the reactor being sufficiently displaced from by high pure nitrogen, add 300mLTiCl4, -20 DEG C are cooled to, adds ethyoxyl
Magnesium 7.0g, when being warming up to 40 DEG C under stirring stage by stage, add the compound 2 of DNBP (0.003 mole) and the structure, 6- bis-
(2,6- imino dimethyl benzene) ethylpyridine (0.003 mole), maintains temperature 3 hours, after filtering.Add TiCl4100mL,
110 DEG C are warming up to, is handled three times.Add hexane 60mL washings three times.Solids 6.7g (solid constituent) is obtained, is contained
Ti：3.2%th, Mg：26.6%th, Cl：56.2%.
Embodiment 17
In the reactor being sufficiently displaced from by high pure nitrogen, add 300mLTi (OEt)4, -20 DEG C are cooled to, adds chlorination
Magnesium alcoholate carrier 7.0g (see patent CN1330086A), when being warming up to 40 DEG C under stirring stage by stage, adding DNBP, (0.006 rubs
You), temperature is maintained 2 hours, after filtering.Add TiCl4100mL and the structure compound 2, (2, the 6- diisopropyls of 6- bis-
Phenyl imido) ethylpyridine (0.006 mole), stirs 1 hour, is warming up to 110 DEG C, carry out titanium three times and handle.Add hexane
60mL, washing is three times.Solids 6.3g (solid constituent) is obtained, containing Ti：3.7%th, Mg：23.8%th, Cl：48.6%.
(3) it is catalyzed propylene polymerization experiment
Embodiment 18
Volume is 5L stainless steel cauldron, after gaseous propylene is sufficiently displaced from, adds AlEt32.5mL, methylcyclohexyl
Dimethoxysilane (CHMMS) 5ml makes Al/Si (mol)=25, add above-described embodiment 9 preparation solid constituent 10mg with
And 1.2NL hydrogen, liquid propene 2.5L is passed through, is warming up to 70 DEG C, maintains this temperature 1 hour, cools, bleeds off pressure, discharge to obtain PP trees
Fat, active 48600g/gCat., the isotacticity 97.8% (subordinate list 1) of resulting polymers.
Embodiment 19
With embodiment 18, simply with the solid constituent in the solid constituent alternative embodiment 9 in above-described embodiment 10, as a result
See attached list 1.
Embodiment 20
With embodiment 18, simply with the solid constituent in the solid constituent alternative embodiment 9 in above-described embodiment 11, as a result
See attached list 1.
Embodiment 21
With embodiment 18, simply with the solid constituent in the solid constituent alternative embodiment 9 in above-described embodiment 12.As a result
See attached list 1.
Embodiment 22
With embodiment 18, simply with the solid constituent in the solid constituent alternative embodiment 9 in above-described embodiment 13, as a result
See attached list 1.
Embodiment 23
With embodiment 18, simply with the solid group in solid constituent alternative embodiment 9 synthesized in above-described embodiment 14
Point, as a result see attached list 1.
Embodiment 24
With embodiment 18, simply with the solid group in solid constituent alternative embodiment 9 synthesized in above-described embodiment 15
Point, as a result see attached list 1.
Embodiment 25
With embodiment 18, simply with the solid group in solid constituent alternative embodiment 9 synthesized in above-described embodiment 16
Point, as a result see attached list 1.
Embodiment 26
With embodiment 18, simply with the solid group in solid constituent alternative embodiment 9 synthesized in above-described embodiment 17
Point, as a result see attached list 1.
Embodiment 27
With embodiment 18, simply the polymerization reaction time in embodiment is extended for 2 hours, as a result sees attached list 1.
Embodiment 28
With embodiment 18, simply the polymerization reaction time in embodiment is extended for 3 hours, as a result sees attached list 1.
Embodiment 29
With embodiment 22, simply the polymerization reaction time in embodiment is extended for 2 hours, as a result sees attached list 1.
Embodiment 30
With embodiment 22, simply the polymerization reaction time in embodiment is extended for 3 hours, as a result sees attached list 1.
Embodiment 31
It is simply 7.2NL by the hydrogenation quantitative change in embodiment, concrete outcome sees attached list 1 with embodiment 19.
Embodiment 32
With embodiment 18, simply DNBP will be changed to 2,3- diisobutyls during synthesis of solid catalytic component in embodiment 9
Diethyl succinate, as a result see attached list 1.
Embodiment 33
With embodiment 18, simply DNBP will be changed to 2- isobutyl groups the third two during synthesis of solid catalytic component in embodiment 9
Diethyl phthalate, as a result see attached list 1.
Comparative example 1
The synthesis of catalytic component：In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 4.8g is sequentially added,
Toluene 95mL, epoxychloropropane 4ml, tributyl phosphate (TBP) 12.5mL, 50 DEG C are warming up under stirring, and maintained 2.5 hours,
After solid is completely dissolved, phthalic anhydride 1.4g is added, continues to 1 hour, solution is cooled to less than -25 DEG C, 1 is small
When interior dropwise addition TiCl4, 80 DEG C are to slowly warm up to, gradually separates out solids, adds DNBP (0.006 mole), maintains temperature 1 small
When, after heat filtering, toluene 150mL is added, washing is secondary, obtains solid, adds toluene 100mL, is warming up to 110 DEG C, carries out three
Secondary washing, time are respectively 10 minutes, hexane 60mL, are stirred 30 minutes, add hexane 60mL washings three times.Obtain solids
7.4g (solid constituent), containing Ti：2.3%th, Mg：22.6%th, Cl：51.4%.
Propylene polymerization is tested：Volume is 5L stainless steel cauldron, after gaseous propylene is sufficiently displaced from, is added
AlEt32.5mL, Cyclohexylmethyldimethoxysilane (CHMMS) 5ml make Al/Si (mol)=25, add above-mentioned preparation
Solid constituent 10mg and 1.2NL hydrogen, is passed through liquid propene 2.5L, is warming up to 70 DEG C, maintains this temperature 1 hour, cooling, puts
Pressure, discharge to obtain PP resins, as a result sees attached list 1.
Table 1
It is compound shown in formula I and formula II in embodiment 18 as compound internal electron donor, and only makes in comparative example 1
The compound shown in formula II is internal electron donor, and the preparation of other catalytic components is identical with propylene polymerization condition, can from table 1
See, corresponding catalyst has higher activity and capacity of orientation in embodiment, and the isotactic index of resulting polymers is high, molecule
Amount distribution is wider.In addition, compared with the catalyst in comparative example, present invention gained catalyst activity decay is slower, and hydrogen is adjusted sensitive
Performance is more preferable.
Claims (11)
1. the catalytic component for propylene polymerization, it is characterised in that contain magnesium, titanium, halogen and interior in the catalytic component
Electron donor, and the internal electron donor is the compound internal electron donor of compound shown in formula I and dibasic acid ester, formula I institutes
Show that compound structure is as follows,
In formula I, R and R ' are identical or different, for the C containing substituent or without substituent1~C20Alkyl, C2~C20Alkene
Base or C6~C20Do not contain heteroatomic aryl or selected from pyridine radicals, pyrrole radicals, pyrimidine radicals and quinolyl, and the substituent
Selected from alkyl, hydroxyl and halogen；
R1~R5It is identical or different, it is hydrogen, halogen atom, hydroxyl, alkoxy or the C containing substituent or without substituent1~C12's
Alkyl, C2~C12Alkenyl or C6~C20Aryl；
X is nitrogen.
2. catalytic component according to claim 1, it is characterised in that the dibasic acid ester is the chemical combination as shown in formula II
Thing,
In formula II, R and R ' are identical or different, for the C of the straight chain containing substituent or without substituent, side chain or ring-type1~
C20Alkyl, and the substituent is selected from hydroxyl and halogen；R1~R4It is identical or different, it is hydrogen, halogen atom, hydroxyl, alcoxyl
Base or the C containing substituent or without substituent1~C12Alkyl, C2~C12Alkenyl or C6~C20Aryl.
3. catalytic component according to claim 2, it is characterised in that the dibasic acid ester is selected from phthalic acid diethyl
Ester, dipropyl phthalate, diisobutyl phthalate, n-butyl phthalate, amyl phthalate,
Di-iso-amyl phthalate, the peopentyl ester of phthalic acid two, DHP, dibutyl phthalate (DHP), adjacent benzene
Diformazan dioctyl phthalate, dinonyl phthalate, 2- methylphthalic acids diisobutyl ester, two positive fourth of 2- methylphthalic acids
Ester, 2- propyl group diisobutyl phthalate, 2- propyl group n-butyl phthalate, the isobutyl of 2- butyl phthalic acid two
Ester, 2- butyl n-butyl phthalate, 4- propyl group diisobutyl phthalate, two positive fourth of 4- butyl phthalic acid
Ester, 2- chloro-o-phthalic acids diisobutyl ester, 2- chloro-o-phthalic acids di-n-butyl, 4- chloro-o-phthalic acids diisobutyl ester, 4- chlorine
One or more in n-butyl phthalate, 4- methoxyl group n-butyl phthalates.
4. catalytic component according to claim 1, it is characterised in that compound shown in the formula I is selected from 2,6- bis-
(benzene is sub- by (2,6- imino dimethyl benzenes) ethylpyridine, 2,6- bis- (2,6- diisopropyls phenyl imido) ethylpyridine, 2,6- bis-
Amido) ethylpyridine, 2,6- bis- (2- naphthalenes imido grpup) ethylpyridine, 2,6- bis- (1- naphthalenes imido grpup) ethylpyridine, (the fourths of 2,6- bis-
Imido grpup) ethylpyridine, 2,6- bis- (own imido grpup) ethylpyridine, 2,6- bis- (penta imido grpup) ethylpyridine, (the Xin Ya of 2,6- bis-
Amido) ethylpyridine, 2,6- bis- (benzyl imido grpup) ethylpyridine, 2,6- bis- (4- chlorobenzenes imido grpup) ethylpyridine, (the 4- of 2,6- bis-
Trifluoromethyl phenyl imido) ethylpyridine, 2,6- bis- (2- trifluoromethyls phenyl imido) ethylpyridine, (the chloro- 6- hydroxyls of 2- of 2,6- bis-
Base phenyl imido) ethylpyridine, 2,6- bis- (8- quinoline imido grpup) ethylpyridine, 2,6- bis- (4- quinoline imido grpup) ethyl pyrrole
(benzene is sub- by pyridine, 2,6- bis- (3- quinoline imido grpup) ethylpyridine, 2,6- bis- (2,4,6- trimethylbenzenes imido grpup) ethylpyridine, 2-
Amido) ethyl -6- (2,6- imino dimethyl benzenes) ethylpyridine, (2,6- diisopropyl benzenes are sub- by 2- (phenyl imido) ethyls -6-
Amido) ethylpyridine, 2- (phenyl imido) ethyls -6- (to chlorobenzene imido grpup) ethylpyridine, 2- (2,6- diisopropyl benzene imines
Base) ethyl -6- (2,6- imino dimethyl benzenes) ethylpyridine, 2- (to chlorobenzene imido grpup) ethyl -6- (2,6- diisopropyl benzenes
Imido grpup) ethylpyridine, 2- (2- hydroxyl -4- chlorobenzenes imido grpup) ethyl -6- (to chlorobenzene imido grpup) ethylpyridine, 2,6- bis-
(2- hydroxyls phenyl imido) ethylpyridine, 2,6- bis- (2- ethyls phenyl imido) ethylpyridine, (the 4- ethylo benzene imines of 2,6- bis-
Base) ethylpyridine, 2,6- bis- (2- propyl group phenyl imido) ethylpyridine, 2,6- bis- (4- propyl group phenyl imido) ethylpyridine, 2,
One or more in 6- bis- (2- butyl phenyl imido) ethylpyridine, 2,6- bis- (4- butyl phenyl imido) ethylpyridine.
5. catalytic component according to claim 1, it is characterised in that the dibasic acid ester is fatty group dibasic acid.
6. catalytic component according to claim 5, it is characterised in that the dibasic acid ester is dimethyl malenate, third
Diethyl adipate, 2- diethyl isopropyls, 2- normal-butyl -2- iso-butyl diethyl malonates, 2- n-butylmalonic acids
Diethylester, 2- iso-butyl diethyl malonates, 2,2- diisobutyls diethyl malonate, 2- isopentyl-diethyl malonate, third
Dipropyl malona-te, dibutyl malonate, dimethyl succinate, diethyl succinate, 2,3- diisopropyls diethyl succinate, 2,
3- diisobutyls diethyl succinate, 2,3- di-n-butyls diethyl succinate, dipropyl succinate, dibutyl succinate, penta
Acid dimethyl, ethyl glutarate, 3- propyl group ethyl glutarate, glutaric acid dipropyl, dibutyl glutarate, adipic acid two
Methyl esters, diethylene adipate, dipropyl adipate, dibutyl adipate, dimethyl sebacate, diethyl sebacate, decanedioic acid
Dipropyl, dibutyl sebacate.
7. the catalytic component according to any one in claim 1~6, it is characterised in that compound shown in formula I exists
Weight percentage in the catalytic component is 0.01~20%；Weight of the dibasic acid ester in the catalytic component
It is 0.01~20% to measure percentage composition.
8. catalytic component according to claim 7, it is characterised in that compound shown in formula I is in the catalyst group
Weight percentage in point is 1~15%.
9. catalytic component according to claim 8, it is characterised in that compound shown in formula I is in the catalyst group
Weight percentage in point is 2~10%.
10. catalytic component according to claim 7, it is characterised in that the dibasic acid ester is in the catalytic component
In weight percentage be 1~15%.
11. a kind of catalyst, including component a and b as described below, and selectable component c, wherein：
a：As above the catalytic component in claim 1~10 described in any one, b：Co-catalyst organo-aluminum compound, c：Outside
Electron donor organo-silicon compound.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410169052.1A CN105085749B (en) | 2014-04-24 | 2014-04-24 | Catalytic component and its catalyst for propylene polymerization |
| KR1020167032804A KR102293704B1 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization and catalyst thereof |
| MYPI2016703904A MY176619A (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 |
| PCT/CN2015/077381 WO2015161827A1 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization and catalyst thereof |
| US15/306,255 US10208145B2 (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 |
| JP2016564188A JP6804302B2 (en) | 2014-04-24 | 2015-04-24 | Catalyst components for olefin polymerization and catalysts containing them |
| SG11201608921YA SG11201608921YA (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization and catalyst containing the same |
| RU2016145949A RU2688689C2 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerisation and catalyst containing it |
| SA516380135A SA516380135B1 (en) | 2014-04-24 | 2016-10-24 | Catalyst Component for Olefin Polymerization, and Catalyst Containing the Same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410169052.1A CN105085749B (en) | 2014-04-24 | 2014-04-24 | Catalytic component and its catalyst for propylene polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105085749A CN105085749A (en) | 2015-11-25 |
| CN105085749B true CN105085749B (en) | 2017-12-19 |
Family
ID=54567143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410169052.1A Active CN105085749B (en) | 2014-04-24 | 2014-04-24 | Catalytic component and its catalyst for propylene polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105085749B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759673B (en) * | 2019-10-21 | 2023-02-28 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization, catalyst component and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405192A (en) * | 2002-11-11 | 2003-03-26 | 中山大学 | Titanium-nickel acetylacetonate composite catalyst for preparing branched polyethylene and its preparation method |
| CN1884311A (en) * | 2006-05-22 | 2006-12-27 | 中国科学院上海有机化学研究所 | Mono-active center Ziegler-Natta catalyst for olefinic polymerization |
| CN101280031A (en) * | 2007-04-06 | 2008-10-08 | 中国石油化工股份有限公司 | Catalyst system for preparing dual-peak or widely distributed polyethylene and its application |
| EP2093315A1 (en) * | 2008-02-22 | 2009-08-26 | Total Petrochemicals Research Feluy | Fibres and nonwoven prepared from polypropylene having a large dispersity index |
| CN102850391A (en) * | 2011-07-01 | 2013-01-02 | 中国石油化工股份有限公司 | Salicylaldehyde pyridine imido titanium trichloride complex, its preparation method and application thereof, and polymerization method of ethene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100714847B1 (en) * | 2001-07-30 | 2007-05-04 | 삼성토탈 주식회사 | Olefin Polymerization Catalyst and Polymerization Process Using the Same |
-
2014
- 2014-04-24 CN CN201410169052.1A patent/CN105085749B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405192A (en) * | 2002-11-11 | 2003-03-26 | 中山大学 | Titanium-nickel acetylacetonate composite catalyst for preparing branched polyethylene and its preparation method |
| CN1884311A (en) * | 2006-05-22 | 2006-12-27 | 中国科学院上海有机化学研究所 | Mono-active center Ziegler-Natta catalyst for olefinic polymerization |
| CN101280031A (en) * | 2007-04-06 | 2008-10-08 | 中国石油化工股份有限公司 | Catalyst system for preparing dual-peak or widely distributed polyethylene and its application |
| EP2093315A1 (en) * | 2008-02-22 | 2009-08-26 | Total Petrochemicals Research Feluy | Fibres and nonwoven prepared from polypropylene having a large dispersity index |
| CN102850391A (en) * | 2011-07-01 | 2013-01-02 | 中国石油化工股份有限公司 | Salicylaldehyde pyridine imido titanium trichloride complex, its preparation method and application thereof, and polymerization method of ethene |
Non-Patent Citations (1)
| Title |
|---|
| 树枝状烯烃聚合催化剂研究进展;王俊 等;《石油学报（石油加工）》;20131031;第29卷(第5期);第920-928页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105085749A (en) | 2015-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103665201B (en) | A kind of catalytic component for olefinic polymerization and preparation method thereof and catalyst system and catalyzing | |
| CN105085747B (en) | Catalytic component and its catalyst for propylene polymerization | |
| JP6804302B2 (en) | Catalyst components for olefin polymerization and catalysts containing them | |
| CN102453147B (en) | Catalyst component, catalyst and method for olefin polymerization | |
| CN105085746B (en) | Catalytic component and its catalyst for propylene polymerization | |
| CN103012625A (en) | Olefin polymerization catalyst ingredient, preparation method and use of the olefin polymerization catalyst ingredient, catalyst system, use of the catalyst system, and olefin polymerization method | |
| CN105492469B (en) | Catalytic component for olefinic polymerization | |
| CN107868152A (en) | A kind of catalytic component, catalyst and its application for olefinic polymerization | |
| CN108727524A (en) | Internal electron donor compound and catalyst for catalyzing propylene polymerization | |
| CN105085749B (en) | Catalytic component and its catalyst for propylene polymerization | |
| CN110144022A (en) | The industrial production process of Ziegler-Natta catalyst | |
| CN101104589A (en) | Urethane compound for preparing olefin polymerization catalyst | |
| CN104610476B (en) | Catalysis system for olefin polymerization reaction | |
| CN107987196A (en) | For catalyst constituent for olefinic polymerization and its catalyst | |
| CN101195668B (en) | Supported main catalyst for propylene polymerization and preparation method thereof | |
| CN107868147A (en) | A kind of catalytic component, catalyst and its application for olefinic polymerization | |
| CN107868149A (en) | A kind of catalytic component, catalyst and its application for olefinic polymerization | |
| CN102453149B (en) | Olefin polymerization catalyst component, olefin polymerization catalyst and olefin polymerization method | |
| CN101787088B (en) | Polymerization catalyst of internal electron donor prepared from phosphorus-substituted sulfonyl compound and preparation and application thereof | |
| CN107987189A (en) | A kind of catalyst component for olefin and its preparation method and application | |
| EP3268397A1 (en) | Catalyst components for the polymerization of olefins | |
| CN1318457C (en) | Catalyst component for olefinic polymerization and its catalyst | |
| CN102040485A (en) | Diether compound for preparing olefin polymerization catalyst | |
| CN108084303A (en) | For the catalytic component of olefinic polymerization | |
| CN109553704A (en) | A kind of catalytic component, catalyst and application for olefinic polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |