CN103694385A - Propylene polymerization catalytic component and catalyst thereof - Google Patents
Propylene polymerization catalytic component and catalyst thereof Download PDFInfo
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- CN103694385A CN103694385A CN201210366655.1A CN201210366655A CN103694385A CN 103694385 A CN103694385 A CN 103694385A CN 201210366655 A CN201210366655 A CN 201210366655A CN 103694385 A CN103694385 A CN 103694385A
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Abstract
The invention discloses a propylene polymerization catalytic component and a catalyst thereof. The propylene polymerization catalytic component is mainly composed of a spherical magnesium halide alcohol compound, titanium halide and an internal electron donor compound, wherein the internal electron donor compound is a mixture of diphenyl amide represented by the formula (I) and diester represented by the formula (II), and the molar ratio of diphenyl amide to diester is 0.5:1 to 2.2:1; according to the weight percentage, the catalytic component contains 10-25% of magnesium, 1-10% of titanium, 40-60% of halogen and 1-30% of an internal donor. The propylene polymerization catalyst is composed of the catalytic component, an alkyl aluminum compound and an organosilicon compound; and when being used in propylene (co) polymerization, the catalyst has higher catalytic activity, good hydrogen response, and allows a polymer to maintain high stereospecificity and broad molecular weight distribution.
Description
Technical field
The present invention relates to a kind of propylene polymerization catalyst component and catalyzer thereof, be specifically related to propylene polymerization catalyst component and catalyzer thereof containing solid titanium.
Background technology
Polypropylene is a kind of important polyolefin products.Most of alkene, particularly propylene (being total to) polymerization is caused by take the Ziegler-Natta catalyst that magnesium, titanium, halogen and electron donor be component, and the polymerisate taxis obtaining is good.In catalyst component, internal electron donor is very important component, very large on the impact of catalyst performance.
Existing bibliographical information multiple internal electron donor, if monoesters class, diester class, two ethers, diones, succinate compound and alkoxide etc. are containing the compound of carbonyl, CN85100997A has adopted diisobutyl phthalate; CN1473809, CN1376722, CN1298887, CN1268957, CN1143651, CN1141303, CN1141285, CN1066723, EP0728770, EP0728724, EP0361493, US5095153, US5068213, US4978648 etc. have adopted 1,3-diether compound, the substituting group that the substituting group that in this compound, on carbon atom, spatial volume is large and symmetry are higher is conducive to the raising of catalytic activity and polymkeric substance degree of isotacticity; CN101628951A has adopted succinic diamide compounds; CN1681853, CN1398270, CN1313869, US0050014631, WO00/63261, WO2004024785 etc. have adopted succinate compounds, the catalyzer of preparing with this compound is during for propylene polymerization, catalyst activity obviously increases, and gained polypropylene molecule amount distributes and obviously widens.
Summary of the invention
A kind of propylene polymerization catalyst component and catalyzer thereof have been the object of this invention is to provide.
Propylene polymerization catalyst component of the present invention, mainly by spherical magnesium halide alcohol polymer, halogenated titanium, internal electron donor compound, formed, it is characterized in that internal electron donor compound is the mixture of two phenyl amides of formula I and the diester of formula II, both mol ratios are 0.5:1～2.2:1
Substituent R in formula I
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
12identical or different, be selected from H, halogen atom, C
1～C
20straight or branched alkyl, C
3～C
20cycloalkyl, C
6～C
20aryl or C
7～C
20aralkyl;
Substituent R in formula II
13, R
14, R
15, R
16, R
17, R
18identical or different, be selected from H, C
1～C
20straight or branched alkyl;
By weight percentage, catalyst component comprises 10～25% magnesium, 1～10% titanium, 40～60% halogens and 1～30% internal electron donor.
The synthetic of described general formula compound (I) can adopt known method, and main process is: by p-methylbenzoic acid or derivatives thereof and excessive dehydrated alcohol reflux 1～25 hour under acidic conditions, preferably 2～20 hours; Excessive ethanol is removed in distillation, obtains crude product and adds excessive hydrazine hydrate or derivatives thereof to it, stirring and refluxing 1～25 hour, preferably 2～20 hours, filtration, washing, dry, recrystallization; Again by solids and Benzoyl chloride or derivatives thereof reflux 1～15 hour in anhydrous pyridine solution, preferably 2～10 hours, through cooling, filter, washing, dry, recrystallization obtains.
The example of suitable general formula compound (I) includes but not limited to:
Two-(2 '-aminomethyl phenyl) hydrazides, two-(3 '-aminomethyl phenyl)-hydrazides, two-(4 '-aminomethyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(3 '-aminomethyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(4 '-aminomethyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(2 '-ethylphenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(3 '-ethylphenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(4 '-ethylphenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(2 '-ethylphenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(3 '-ethylphenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(4 '-ethylphenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(2 '-ethylphenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(3 '-ethylphenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(4 '-ethylphenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(2 '-propyl group phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(3 '-propyl group phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(4 '-propyl group phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(2 '-propyl group phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(3 '-propyl group phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(4 '-propyl group phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(2 '-propyl group phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(3 '-propyl group phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(4 '-propyl group phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(2 '-isopropyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(3 '-isopropyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(4 '-isopropyl phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(2 '-isopropyl phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(3 '-isopropyl phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(4 '-isopropyl phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(2 '-isopropyl phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(3 '-isopropyl phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(4 '-isopropyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(2 '-butyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(3 '-butyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(4 '-butyl phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(2 '-butyl phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(3 '-butyl phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(4 '-butyl phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(2 '-butyl phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(3 '-butyl phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(4 '-butyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(2 '-isobutyl phenenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(3 '-isobutyl phenenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(4 '-isobutyl phenenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(2 '-isobutyl phenenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(3 '-isobutyl phenenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(4 '-isobutyl phenenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(2 '-isobutyl phenenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(3 '-isobutyl phenenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(4 '-isobutyl phenenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(2 '-tert-butyl-phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(3 '-tert-butyl-phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(4 '-tert-butyl-phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(2 '-tert-butyl-phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(3 '-tert-butyl-phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(4 '-tert-butyl-phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(2 '-tert-butyl-phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(3 '-tert-butyl-phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(4 '-tert-butyl-phenyl)-hydrazides, two-(2 '-ethylphenyl)-hydrazides, two-(3 '-ethylphenyl)-hydrazides, two-(4 '-ethylphenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(3 '-ethylphenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(4 '-ethylphenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(2 '-propyl group phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(3 '-propyl group phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(4 '-propyl group phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(2 '-propyl group phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(3 '-propyl group phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(4 '-propyl group phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(2 '-propyl group phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(3 '-propyl group phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(4 '-propyl group phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(2 '-isopropyl phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(3 '-isopropyl phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(4 '-isopropyl phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(2 '-isopropyl phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(3 '-isopropyl phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(4 '-isopropyl phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(2 '-isopropyl phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(3 '-isopropyl phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(4 '-isopropyl phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(2 '-butyl phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(3 '-butyl phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(4 '-butyl phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(2 '-butyl phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(3 '-butyl phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(4 '-butyl phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(2 '-butyl phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(3 '-butyl phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(4 '-butyl phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(2 '-isobutyl phenenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(3 '-isobutyl phenenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(4 '-isobutyl phenenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(2 '-isobutyl phenenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(3 '-isobutyl phenenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(4 '-isobutyl phenenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(2 '-isobutyl phenenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(3 '-isobutyl phenenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(4 '-isobutyl phenenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(2 '-tert-butyl-phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(3 '-tert-butyl-phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(4 '-tert-butyl-phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(2 '-tert-butyl-phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(3 '-tert-butyl-phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(4 '-tert-butyl-phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(2 '-tert-butyl-phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(3 '-tert-butyl-phenyl)-hydrazides or 1-(4 '-ethylphenyl)-2-(4 '-tert-butyl-phenyl)-hydrazides.
Formula II compound is selected from wherein a kind of of diisobutyl phthalate, diethyl phthalate or n-butyl phthalate, and can be directly commercially available.
Magnesium halide alcohol adduct in catalyst component meets formula M g (OR')
mx
(2-m)nROH, in formula, R' is C
1～C
20alkyl, aralkyl or aryl; X is halogen; M is the integer of 0≤m<2; N is decimal or the integer of 0<n<6; R is C
1～C
20alkyl, aralkyl or aryl.
Magnesium halide in magnesium halide alcohol adduct is selected from a kind of in magnesium dichloride, dibrominated magnesium, chloro magnesium methylate or chloro magnesium ethylate, preferably magnesium dichloride; Alcohol in magnesium halide alcohol adduct is selected from a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol, preferred alcohol.
The preparation of magnesium halide alcohol adduct adopts magnesium halide and alcohol to heat altogether after melting, and high pressure ejection or high-speed stirring are solidified into microballoon and obtain in heat-eliminating medium, and concrete steps are referring to the associated description in CN1091748A.
Halogenated titanium general formula in catalyst component is Ti (OR)
px
(4-p), in formula, R is C
1～C
20alkyl, aryl or aralkyl; X is halogen; P is the integer of 0≤p < 4.Specifically be selected from wherein a kind of of purity titanium tetraethoxide, four titanium butoxide, chloro tri-alkoxy titanium, dichloro dialkoxy titanium, trichlorine titan-alkoxide, titanium tetrachloride or titanium tetrabromide, preferably titanium tetrachloride.
In addition, the invention provides a kind of preparation method of described catalyst component, process comprises: (1) joins spherical magnesium halide alcohol polymer-50～20 ℃, preferably, in the halogenated titanium of-30～0 ℃, reacts 1～4 hour, and the mol ratio of magnesium and titanium is 1:5～1:50; (2) be warming up to 30～80 ℃, add the mixture of two phenyl amides and diester, mol ratio is 0.5:1～2.2:1, preferred 1:1, and the mol ratio of magnesium and internal electron donor mixture is 2:1～15:1; (3) be warming up to again 100～150 ℃, react 1～4 hour; (4) add the titanium compound with step (1) same amount after filtering, in 110～130 ℃ of reactions 1～4 hour, more after filtration, washing, obtains after dry again.
Above-mentioned catalyst component also needs to add alkylaluminium cpd promotor and external electron donor to form catalyzer for propylene polymerization.Alkylaluminium cpd is selected from the mixture of trialkylaluminium, trialkylaluminium and aluminum alkyl halide or alkyl aluminum hydride, or alkylaluminoxane.
External electron donor can be selected silicoorganic compound, as: trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, methyl-t-butyldimethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane or two (cyclobutylmethyl) dimethoxy silane, preferred Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane or two (cyclobutylmethyl) dimethoxy silane.
With titanium: aluminium: the molar ratio computing between external donor compound, the amount ratio in catalyzer between each component is 1:1～2000:1～50; Be preferably 1:1～500:1～20.
Catalyst component of the present invention, for the equal polymerization of propylene and the copolymerization of propylene and other alkene, can access the polymkeric substance that isotactic index is very high.Meanwhile, do not get rid of yet and be applicable to produce polyethylene and ethene and alpha-olefin as the copolymerization of propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene or 1-octene.
During for propylene polymerization, can adopt the whole bag of tricks of the prior art, can in liquid phase or gas phase, carry out, also can under the combination operation of liquid and gas polymerization stage, carry out.Polymerization is carried out at 0～150 ℃ conventionally, and preferably 40～90 ℃, polymerization pressure is 0.01～10MPa.Adopt hydrogen or other compound to control the molecular weight of polymkeric substance.
In catalyst component provided by the invention, two kinds of specific interior electronics of giving are as the efficient component of alkene polypropylene catalyst, during for propylene (being total to) polymerization, catalyzer has higher catalytic activity, and hydrogen response is good, and polymkeric substance keeps high tacticity and wide molecular weight distribution.
Embodiment
Embodiment given below is for the present invention rather than limitation of the present invention are described better.
Testing method
1, polymericular weight and molecular weight distribution MWD: adopt gel permeation chromatography method, with Alliance-GPCV2000, take orthodichlorobenzene and at 135 ℃, measure as solvent.
2, polymkeric substance degree of isotacticity: adopt heptane extraction process to measure (heptane boiling extracting 8 hours), i.e. 1 gram of dry polymer samples, be placed in extractor and use the extracting of boiling heptane after 8 hours, the polymer weight (g) that residuum is dried to constant weight gained is degree of isotacticity with 1 ratio.
3, the mensuration of melt index: measure according to μ PXRZ-400C.
4, the mensuration of titanium percentage composition: according to spectrophotometry.
5, the mensuration of internal electron donor percentage composition: according to the AutosystemXL of PE company gas chromatograph for determination.
Embodiment
One, two phenyl amide compounds is synthetic
Only, with the example that synthesizes of 1-(4 '-aminomethyl phenyl)-2-(4 '-tert-butyl-phenyl)-hydrazides, concrete method is as follows:
(1) synthesizing toluyl hydrazine
10g p-methylbenzoic acid is dissolved in to 200mL dehydrated alcohol completely, and by 5mL H
2sO
4slowly drop in reaction flask stirring and refluxing 20h.Excessive ethanol is removed in distillation, obtains crude product ethyl p-methyl benzoate.In crude product, add excessive hydrazine hydrate (20mL), stirring and refluxing 15h at 80 ℃.Product is filtered, washing, dry, then use recrystallizing methanol, obtain white solid 9.15g, yield 84%.
(2) 1-(4 '-aminomethyl phenyl)-2-(4 '-tert-butyl-phenyl)-hydrazides is synthetic
At 0 ℃, 13.2g is dissolved in 100mL anhydrous pyridine solution, at N toluyl hydrazine
2the lower 4-tert.-butylbenzene formyl chloride 17.3g that drips of protection, drips and finishes rear temperature rising reflux 5h.After reaction finishes, be cooled to room temperature, mixture is slowly poured in 200mL frozen water, occur a large amount of white precipitates.Filter water repetitive scrubbing several, vacuum-drying.Crude product, through recrystallizing methanol, obtains white solid 22.45g, and yield is 78%, m.p.237-238 ℃ of .IR (KBr pellet, cm-1): 3218 (N-H), 2961 (Alkyl-CH), 1635 (C=O), 1540 (C-N), 1499,1277,1114,843,749.
Two, the preparation of catalyzer
Embodiment 1-33
Under anhydrous and oxygen-free condition, by 100mlTiCl
4be added in 500ml round-bottomed flask, be cooled to-20 ℃, add 10gMgCl
22.8CH
3cH
2oH ball type carrier, constant temperature 1h.With 2h, be slowly warming up to 60 ℃, add respectively the mixture 7.4mmol of corresponding two kinds of internal electron donors in table 1, with 2h, be slowly warming up to 120 ℃, constant temperature 2h at 120 ℃.Pump filtrate, again add 100mlTiCl
4, constant temperature 2h at 120 ℃.Pump filtrate, at 50 ℃, each 60ml anhydrous hexane solid ingredient of using, washs 3 times, at normal temperatures, washs 3 times, obtains solid catalyst after vacuum-drying.
Comparative example 1-5
By the method for above-described embodiment, prepare spherical catalyst component, internal electron donor is replaced with to two-(2 '-aminomethyl phenyl) hydrazides, 1-(2 '-aminomethyl phenyl)-2-(3 '-aminomethyl phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(4 '-tert-butyl-phenyl)-hydrazides, phthalic acid two isobutyl fat, the positive fourth fat of phthalic acid two.
Three, propylene polymerization experiment
The catalyzer of above-described embodiment 1-33 and comparative example 1-5 is carried out respectively to propylene polymerization.First, after the stainless steel autoclave of 5L fully being replaced with high pure nitrogen, add AlEt
32.5mmol, external electron donor Cyclohexylmethyldimethoxysilane (CHMMS) 0.1mmol, then add ingredient of solid catalyst 10mg and the 1.2L hydrogen of above-described embodiment 1-33 and comparative example 1-5, and pass into liquid propene 2.3L, be warming up to 70 ℃, reaction 1h.Cooling, pressure release, obtains PP powder.Polymerization result is listed in table 1.
Table 1 propylene polymerization result
Four, vinyl polymerization experiment
Volume is the stainless steel autoclave of 10L, after high pure nitrogen is fully replaced, starts stirring, under nitrogen protection progressively to the catalyst solid constituent and the 5.0mmol promotor AlEt that add 2L hexane, 20mg embodiment 1 gained in still
3be warming up to after 75 ℃, in still, supplement appropriate high-purity hydrogen, making hydrogen partial pressure in still is 0.3Mpa, and in 5 minutes backward stills, make-up ethylene gas makes its dividing potential drop reach 0.75Mpa, the dividing potential drop that maintains ethylene gas is constant, make system temperature keep 80 ℃, after 3 hours, cooling discharge, polymkeric substance, except desolventizing, is obtained to polyethylene 560g after being fully dried.
Five, ethene and copolymerization of propylene experiment
Volume is the stainless steel autoclave of 10L, after high pure nitrogen is fully replaced, starts stirring, under nitrogen protection progressively to the catalyst solid constituent and the 5.0mmol promotor AlEt that add 2L hexane, 20mg embodiment 1 gained in still
3pass into liquid propene 2.5L, be warming up to after 75 ℃, in still, supplement appropriate high-purity hydrogen, making hydrogen partial pressure in still is 0.3Mpa, in 5 minutes backward stills, make-up ethylene gas makes its dividing potential drop reach 0.75Mpa, and the dividing potential drop that maintains ethylene gas is constant, makes system temperature keep 80 ℃, after 3 hours, cooling discharge, except desolventizing, obtains polymer powders 846g after being fully dried by polymkeric substance.
Claims (11)
1. propylene polymerization catalyst component, mainly by spherical magnesium halide alcohol polymer, halogenated titanium, internal electron donor compound, formed, it is characterized in that internal electron donor compound is the mixture of two phenyl amides of formula (I) and the diester of formula II, both mol ratios are 0.5:1～2.2:1
Substituent R in formula (I)
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11, R
12identical or different, be selected from H, halogen atom, C
1～C
20straight or branched alkyl, C
3～C
20cycloalkyl, C
6～C
20aryl or C
7～C
20aralkyl;
Substituent R in formula II
13, R
14, R
15, R
16, R
17, R
18identical or different, be selected from H, C
1～C
20straight or branched alkyl;
By weight percentage, catalyst component comprises 10～25% magnesium, 1～10% titanium, 40～60% halogens and 1～30% internal electron donor.
2. catalyst component according to claim 1, is characterized in that formula (I) compound is selected from two-(2 '-aminomethyl phenyl) hydrazides, two-(3 '-aminomethyl phenyl)-hydrazides, two-(4 '-aminomethyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(3 '-aminomethyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(4 '-aminomethyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(2 '-ethylphenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(3 '-ethylphenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(4 '-ethylphenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(2 '-ethylphenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(3 '-ethylphenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(4 '-ethylphenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(2 '-ethylphenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(3 '-ethylphenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(4 '-ethylphenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(2 '-propyl group phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(3 '-propyl group phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(4 '-propyl group phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(2 '-propyl group phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(3 '-propyl group phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(4 '-propyl group phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(2 '-propyl group phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(3 '-propyl group phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(4 '-propyl group phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(2 '-isopropyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(3 '-isopropyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(4 '-isopropyl phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(2 '-isopropyl phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(3 '-isopropyl phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(4 '-isopropyl phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(2 '-isopropyl phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(3 '-isopropyl phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(4 '-isopropyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(2 '-butyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(3 '-butyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(4 '-butyl phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(2 '-butyl phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(3 '-butyl phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(4 '-butyl phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(2 '-butyl phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(3 '-butyl phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(4 '-butyl phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(2 '-isobutyl phenenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(3 '-isobutyl phenenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(4 '-isobutyl phenenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(2 '-isobutyl phenenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(3 '-isobutyl phenenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(4 '-isobutyl phenenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(2 '-isobutyl phenenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(3 '-isobutyl phenenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(4 '-isobutyl phenenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(2 '-tert-butyl-phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(3 '-tert-butyl-phenyl)-hydrazides, 1-(2 '-aminomethyl phenyl)-2-(4 '-tert-butyl-phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(2 '-tert-butyl-phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(3 '-tert-butyl-phenyl)-hydrazides, 1-(3 '-aminomethyl phenyl)-2-(4 '-tert-butyl-phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(2 '-tert-butyl-phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(3 '-tert-butyl-phenyl)-hydrazides, 1-(4 '-aminomethyl phenyl)-2-(4 '-tert-butyl-phenyl)-hydrazides, two-(2 '-ethylphenyl)-hydrazides, two-(3 '-ethylphenyl)-hydrazides, two-(4 '-ethylphenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(3 '-ethylphenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(4 '-ethylphenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(2 '-propyl group phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(3 '-propyl group phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(4 '-propyl group phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(2 '-propyl group phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(3 '-propyl group phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(4 '-propyl group phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(2 '-propyl group phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(3 '-propyl group phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(4 '-propyl group phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(2 '-isopropyl phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(3 '-isopropyl phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(4 '-isopropyl phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(2 '-isopropyl phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(3 '-isopropyl phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(4 '-isopropyl phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(2 '-isopropyl phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(3 '-isopropyl phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(4 '-isopropyl phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(2 '-butyl phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(3 '-butyl phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(4 '-butyl phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(2 '-butyl phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(3 '-butyl phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(4 '-butyl phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(2 '-butyl phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(3 '-butyl phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(4 '-butyl phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(2 '-isobutyl phenenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(3 '-isobutyl phenenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(4 '-isobutyl phenenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(2 '-isobutyl phenenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(3 '-isobutyl phenenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(4 '-isobutyl phenenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(2 '-isobutyl phenenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(3 '-isobutyl phenenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(4 '-isobutyl phenenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(2 '-tert-butyl-phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(3 '-tert-butyl-phenyl)-hydrazides, 1-(2 '-ethylphenyl)-2-(4 '-tert-butyl-phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(2 '-tert-butyl-phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(3 '-tert-butyl-phenyl)-hydrazides, 1-(3 '-ethylphenyl)-2-(4 '-tert-butyl-phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(2 '-tert-butyl-phenyl)-hydrazides, 1-(4 '-ethylphenyl)-2-(3 '-tert-butyl-phenyl)-hydrazides or 1-(4 '-ethylphenyl)-2-(4 '-tert-butyl-phenyl)-hydrazides.
3. catalyst component according to claim 1, is characterized in that formula (II) compound is selected from wherein a kind of of diisobutyl phthalate, diethyl phthalate or n-butyl phthalate.
4. catalyst component according to claim 1, is characterized in that described magnesium halide alcohol adduct meets formula M g (OR')
mx
(2-m)nROH, in formula, R' is C
1～C
20alkyl, aralkyl or aryl; X is halogen; M is the integer of 0≤m<2; N is decimal or the integer of 0<n<6; R is C
1～C
20alkyl, aralkyl or aryl.
5. catalyst component according to claim 4, is characterized in that magnesium halide in described magnesium halide alcohol adduct is selected from a kind of in magnesium dichloride, dibrominated magnesium, chloro magnesium methylate or chloro magnesium ethylate; Alcohol in magnesium halide alcohol adduct is selected from a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol.
6. catalyst component according to claim 1, is characterized in that described halogenated titanium general formula is Ti (OR)
px
(4-p), in formula, R is C
1～C
20alkyl, aryl or aralkyl; X is halogen; P is the integer of 0≤p < 4.
7. catalyst component according to claim 6, is characterized in that described halogenated titanium is selected from wherein a kind of of purity titanium tetraethoxide, four titanium butoxide, chloro tri-alkoxy titanium, dichloro dialkoxy titanium, trichlorine titan-alkoxide, titanium tetrachloride or titanium tetrabromide.
8. a catalyst for polymerization of propylene that comprises catalyst component described in claim 1, is characterized in that catalyzer forms to comprise:
1) catalyst component claimed in claim 1;
2) alkylaluminium cpd;
3) silicoorganic compound,
With titanium: aluminium: the molar ratio computing between external donor compound, the amount ratio in catalyzer between each component is 1:1～2000:1～50.
9. catalyst for polymerization of propylene according to claim 8, is characterized in that alkylaluminium cpd is selected from the mixture of trialkylaluminium, trialkylaluminium and aluminum alkyl halide or alkyl aluminum hydride, or alkylaluminoxane.
10. catalyst for polymerization of propylene according to claim 8, is characterized in that silicoorganic compound are selected from Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane or two (cyclobutylmethyl) dimethoxy silane.
11. catalyst for polymerization of propylene according to claim 8, is characterized in that in catalyzer, the amount ratio between each component is 1:1～500:1～20.
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| CN105985464A (en) * | 2015-03-05 | 2016-10-05 | 中国石油天然气股份有限公司 | Olefin polymerization solid catalyst component and catalyst thereof |
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