CN103665201A - Catalyst component for olefin polymerization, and preparation method and catalytic system thereof - Google Patents
Catalyst component for olefin polymerization, and preparation method and catalytic system thereof Download PDFInfo
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- CN103665201A CN103665201A CN201210330113.9A CN201210330113A CN103665201A CN 103665201 A CN103665201 A CN 103665201A CN 201210330113 A CN201210330113 A CN 201210330113A CN 103665201 A CN103665201 A CN 103665201A
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Abstract
The invention relates to a catalyst component for olefin polymerization, and a preparation method and a catalytic system thereof. A silane compound is added in the preparation process of the catalyst to form a catalytic polymerization reaction system. The catalyst has the characteristics of high activity and orientation ability, and slow decay of activity.
Description
Technical field
The present invention relates to manufacture of polyolefins technical field.More particularly, the present invention relates to a kind of Catalysts and its preparation method and catalyst system of olefinic polymerization.
Background technology
Since the fifties, the research and development of propylene polymerization 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 is that carrier, monoesters or aromatic dibasic acid ester are the TiCl that internal electron donor, silane are external electron donor to the magnesium chloride of the third generation
4eDMgCl
2/ AlR
3eD system, the catalytic polymerization activity of catalyzer and gained polypropylene degree of isotacticity height are all greatly improved.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 composition in catalyst component.With the development of electron donor compound, polyolefin catalyst also constantly updates thereupon.
At present, multiple electron donor compound is disclosed, such 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 be referring to US Patent No. 4784983.The disclosed component for olefin polymerization catalyst of US Patent No. 4971937 and European patent EP 0728769, special 1 of two ether groups that contain have been adopted, 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.The special dibasic aliphatic carboxylic acid ester compound of one class is disclosed again thereafter, as (referring to WO98/56830, WO98/56834, WO01/57099, WO01/63231 and WO00/55215) such as succinate, malonic ester, glutarates, the use of this class electron donor compound not only can improve the activity of catalyzer, and the molecular weight distribution of gained propene polymer is obviously widened.
Yet, the above-mentioned disclosed binary aromatic carboxylic acid's ester compound of above-mentioned employing, contain 1 of two ether groups, catalyzer for olefinic polymerization prepared by 3-diether compound and dibasic aliphatic carboxylic acid ester compound all exists certain defect in actual applications, for example adopt the catalytic activity of catalyzer of aromatic dicarboxylic acids's ester compound lower, and the molecular weight distribution of resulting polymers is also narrower; Adopt 1, although the catalyzer activity of 3-diether compound is higher, and the susceptibility of catalyzer to hydrogen tune, the narrow molecular weight distribution of resulting polymers, is unfavorable for the exploitation of the different trades mark of polymkeric substance; And adopt the catalytic activity of catalyzer of recent disclosed dibasic aliphatic carboxylicesters still on the low side, and when not adopting external electron donor component, the degree of isotacticity of resulting polymers is lower, and hydrogen response is also poor.The decay of activity of catalyzer is very fast simultaneously, is unfavorable for the long period application of catalyzer.
In prior art, although disclose a large amount of silane compounds, for example: Chinese patent 1939939A has reported take the manufacture method of the propene polymer that alkoxysilane compound containing trialkylsilyl group in molecular structure is external electron donor, in the molecular structure of this compounds, contain three alkoxyl groups, typical compound comprises 1, 1, 1-trimethylammonium-3, 3, 3-triethoxy two silicon propane (TMTEDSP), 1, 1, 1-trimethylammonium-4, 4, 4-triethoxy two silicon propane (TMTEDSB), 1, 1, 1-trimethylammonium-5, 5, 5-triethoxy two silicon propane (TMTEDSPN), 1, 1, 1-trimethylammonium-3, 3, 3-trimethoxy two silicon propane (TMTMDSP) etc., can obtain high laws, the propene polymer of high melt flow index.WO00/63261 discloses the silicane external donor compound of a class for olefinic polymerization, and general formula is R1
ar2
b(OR
3)
c, the integer that wherein c is 1 ~ 3 and (a+b+c) be 4, its preferred external electron donor comprises Cyclohexyl Methyl Dimethoxysilane (CHMMS) and cyclohexyl trimethoxy silane etc., during for propylene polymerization, can obtain the polymeric articles of high isotactic.
But these silane compounds are mostly as external electron donor, be applied at present catalyzer preparation and less as the research report of internal electron donor aspect.
Toho(east nation titanium) company discloses a kind of silane compound in 2005 in its patent JP20050250579, find that the magnesium alcohol catalyst through these compound treatment has the feature of long-acting catalytic activity, the decay of activity of catalyzer is slower, but preparation technology is more loaded down with trivial details, need to first prepare catalyzer, and then use compound treatment.
Summary of the invention
The object of the invention is to for addressing the above problem, the invention provides a kind of catalyzer for olefinic polymerization, the particularly catalyzer of propylene polymerization.In catalyst preparation process, add the silane compound of a class as shown in following general formula I, formed novel catalytic polymerization system.This catalyzer has higher activity and orientation property, the feature that decay of activity is slower.
Technical scheme of the present invention is:
For a catalyst component for olefinic polymerization, it take magnesium, titanium, halogen and internal electron donor as main component, and described internal electron donor comprises the silane compound as shown in general formula I,
General formula I
R1 in formula, R2, R3, R4 are identical or different, are the alkyl of C1 ~ C20 or the alkyl with vinyl of C2 ~ C20; R5, R6 are identical or different, are the alkyl of C1 ~ C6 or the aralkyl of C6 ~ C20 or alkaryl; A is that one or more replacements or unsubstituted methylene radical, the cycloalkyl of C4 ~ C20 are, the fragrant cyclic group of C5 ~ C20 or condensed ring aromatic base; Integer in n=0 ~ 6.
Given silane compound is selected from two (the triallyl silica methyl) fluorenes of one or more in following compound: 9,9-, 2-sec.-propyl-2-isopentyl-1, two (triallyl siloxy) propane of 3-, 2-allyl group-3-(trimethyl silicane methylene radical)-Isosorbide-5-Nitrae-bis-(triallyl siloxy) butane, 2-propyl group-2-isopentyl-1, two (triallyl siloxy) propane of 3-, 2-allyl group-3-butyl-Isosorbide-5-Nitrae-bis-(triallyl siloxy) butane, 2-propyl group-3-butyl-Isosorbide-5-Nitrae-bis-(triallyl siloxy) butane, 2,3-dibutyl-Isosorbide-5-Nitrae-bis-(triallyl siloxy) butane, 2-ethyl-2-isopentyl-1, two (triallyl siloxy) propane of 3-, 2-sec.-propyl-2-butyl-1, two (triallyl siloxy) propane of 3-, 2,2-dibutyl-1, two (triallyl siloxy) propane of 3-, 3-sec.-propyl-2, two (triallyl siloxy) pentanes of 4-, 3-isopentyl-2, two (triallyl siloxy) pentanes of 4-, 3-methyl-2, two (triallyl siloxy) pentanes of 4-, 3-ethyl-2, two (triallyl siloxy) pentanes of 4-, 3-sec.-propyl-2, two (triallyl siloxy) pentanes of 4-, 3-isopentyl-2, two (triallyl siloxy) pentanes of 4-, 3-butyl-2, two (triallyl siloxy) pentanes of 4-, 3-Bian Ji-2, two (triallyl siloxy) pentanes of 4-, 1,3-phenylbenzene-1, two (triallyl siloxy) propane of 3-, 1,3-phenylbenzene-2-ethyl-1, two (triallyl siloxy) propane of 3-, 1,3-phenylbenzene-2-isopentyl-1, two (triallyl siloxy) propane of 3-, 1,3-phenylbenzene-2-butyl-1, two (triallyl siloxy) propane of 3-, 1-methyl-2-butyl-3-phenyl-1, two (triallyl siloxy) propane of 3-, 1-methyl-3-phenyl-1, two (triallyl siloxy) propane of 3-, 1,2-dimethyl-3-phenyl-1, two (triallyl siloxy) propane of 3-, 1-methyl-2-sec.-propyl-3-phenyl-1, two (triallyl siloxy) propane of 3-, 1-methyl-3-phenyl-1, two (triallyl siloxy) propane of 3-, two (triallyl siloxy) propane of 1-methyl-2-ethyl-3-phenyl-1 and 3-.
Described internal electron donor also comprises one or more in following compound: diatomic alcohol acid ester cpds, diether compound, dibasic aliphatic carboxylic acid ester compound and aromatic polycarboxylic acid esters compound.
Described diatomic alcohol acid ester cpds is one or more in following compound preferably: 2, 4-dibenzoyl oxygen base pentane, 3-methyl-2, 4-dibenzoyl oxygen base pentane, 3-ethyl-2, 4-dibenzoyl oxygen base pentane, 3, 5-dibenzoyl oxygen base heptane, 4-ethyl-3, 5-dibenzoyl oxygen base heptane, 3-propyl group-1, 2-bis-(2-isopropyl benzene methanoyl) benzene, 3-methyl isophthalic acid, 2-bis-(2-isopropyl benzene methanoyl) benzene, 3-sec.-propyl-1, 2-dibenzoyl oxygen base benzene, 9, 9 '-dibenzoyl oxygen methyl fluorenes, 2-sec.-propyl-2-isopentyl-1, 3-dibenzoyl oxygen base propane, 4-methyl-3, 5-dibenzoyl oxygen base heptane or 4-sec.-propyl-3, 5-dibenzoyl oxygen base heptane.
Described diether compound is selected from one or more in following compound: 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isobutyl--1,3-Propanal dimethyl acetal or 9,9-dimethoxy methyl fluorenes.
Described dibasic aliphatic carboxylic acid ester compound is selected from one or more in following compound: dibutyl succinate, 2-diethyl butylmalonate, ethyl glutarate or pentanedioic acid dibutylester.
Described aromatic polycarboxylic acid esters compound is selected from one or more in following compound: n-butyl phthalate, diethyl phthalate, diisobutyl phthalate, 3-methyl-dibutyl phthalate, amyl phthalate or dinoctyl phthalate.
Above-mentioned catalyst component can adopt following two kinds of methods preparation:
Method one:
A) magnesium halide is dissolved in to organic epoxy compounds and organo phosphorous compounds and makes homogeneous solution, in solvent system, add or do not add inert diluent; Inert diluent is preferably non-polar solvent, more preferably toluene;
B) above-mentioned homogeneous solution titanium tetrahalide or derivatives thereof is mixed, add precipitation additive in reaction system, solids is separated out;
C) internal electron donor is attached on solids, then processes with titanium tetrahalide or inert diluent, then with the silane compound shown in above-mentioned general formula I, process, obtain comprising the solid catalyst of titanium, magnesium, halogen and internal electron donor.
Step a) described in organo phosphorous compounds be that phosphate compounds is one or more the mixture in tributyl phosphate, three iso-butyl ester of phosphoric acid, tricresyl phosphate fourth monooctyl ester, triethyl phosphate or TNPP tri n pentyl phosphate.
Step b) precipitation additive described in is selected from one or more in following compound: organic acid anhydride, organic acid, ether, ketone, diol ester, ethers.The preferred diacetyl oxide of organic dianhydride, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE or pyromellitic acid anhydride; The preferred acetic acid of organic acid, propionic acid, butyric acid, acrylic or methacrylic acid; The preferred acetone of ketone, methylethylketone or benzophenone; The preferred methyl ether of ether, ether, propyl ether, butyl ether or amyl ether; Diol ester preferably 2,4-dibenzoyl oxygen base pentane, 3-ethyl-2,4-dibenzoyl oxygen base pentane, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal or 9,9-dimethoxy methyl fluorenes.
Step c) described internal electron donor is selected from one or more mixing of following compound: silane compound of the present invention, diatomic alcohol acid ester cpds, diether compound and dibasic aliphatic carboxylic acid ester compound and aromatic polycarboxylic acid esters compound.
Described diatomic alcohol acid ester cpds is one or more in following compound preferably: 2, 4-dibenzoyl oxygen base pentane, 3-methyl-2, 4-dibenzoyl oxygen base pentane, 3-ethyl-2, 4-dibenzoyl oxygen base pentane, 3, 5-dibenzoyl oxygen base heptane, 4-ethyl-3, 5-dibenzoyl oxygen base heptane, 3-propyl group-1, 2-bis-(2-isopropyl benzene methanoyl) benzene, 3-methyl isophthalic acid, 2-bis-(2-isopropyl benzene methanoyl) benzene, 3-sec.-propyl-1, 2-dibenzoyl oxygen base benzene, 9, 9 '-dibenzoyl oxygen methyl fluorenes, 2-sec.-propyl-2-isopentyl-1, 3-dibenzoyl oxygen base propane, 4-methyl-3, 5-dibenzoyl oxygen base heptane or 4-sec.-propyl-3, 5-dibenzoyl oxygen base heptane,
Described diether compound is selected from one or more in following compound: 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isobutyl--1,3-Propanal dimethyl acetal or 9,9-dimethoxy methyl fluorenes.
Described dibasic aliphatic carboxylic acid ester compound is selected from one or more in following compound: dibutyl succinate, 2-diethyl butylmalonate, ethyl glutarate or pentanedioic acid dibutylester.
Described aromatic polycarboxylic acid esters compound is selected from one or more in following compound: n-butyl phthalate, diethyl phthalate, diisobutyl phthalate, 3-methyl-dibutyl phthalate, amyl phthalate or dinoctyl phthalate.
Method two:
By magnesium halide or organo-magnesium compound, alcohol compound and titanate ester or halogenated titanium compound abundant mix and blend in inert solvent, heating is cooling afterwards to be obtained ball-type carrier or adds inert solvent to obtain uniform alcohol adduct solution.Above-mentioned carrier or homogeneous solution are mixed with titanium tetrahalide or derivatives thereof, in temperature, it is-80～0 ℃, at preferably-40～-10 ℃, maintaining for some time post-heating heats up, add internal electron donor, with titanium tetrahalide or inert diluent, process again, then use the compound treatment of general formula I, finally by the solid catalyst that obtains comprising the compositions such as titanium, magnesium, halogen, electron donor after filtering, wash, being dried.
The preferred toluene of inert solvent described in method two, described internal electron donor is selected from one or more mixing of following compound: silane compound of the present invention, diatomic alcohol acid ester cpds, diether compound and dibasic aliphatic carboxylic acid ester compound and aromatic polycarboxylic acid esters compound.
Described diatomic alcohol acid ester cpds is one or more in following compound preferably: 2, 4-dibenzoyl oxygen base pentane, 3-methyl-2, 4-dibenzoyl oxygen base pentane, 3-ethyl-2, 4-dibenzoyl oxygen base pentane, 3, 5-dibenzoyl oxygen base heptane, 4-ethyl-3, 5-dibenzoyl oxygen base heptane, 3-propyl group-1, 2-bis-(2-isopropyl benzene methanoyl) benzene, 3-methyl isophthalic acid, 2-bis-(2-isopropyl benzene methanoyl) benzene, 3-sec.-propyl-1, 2-dibenzoyl oxygen base benzene, 9, 9 '-dibenzoyl oxygen methyl fluorenes, 2-sec.-propyl-2-isopentyl-1, 3-dibenzoyl oxygen base propane, 4-methyl-3, 5-dibenzoyl oxygen base heptane or 4-sec.-propyl-3, 5-dibenzoyl oxygen base heptane.
Described diether compound is selected from one or more in following compound: 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isobutyl--1,3-Propanal dimethyl acetal or 9,9-dimethoxy methyl fluorenes.
Described dibasic aliphatic carboxylic acid ester compound is selected from one or more in following compound: dibutyl succinate, 2-diethyl butylmalonate, ethyl glutarate or pentanedioic acid dibutylester.
Described aromatic polycarboxylic acid esters compound is selected from one or more in following compound: n-butyl phthalate, diethyl phthalate, diisobutyl phthalate, 3-methyl-dibutyl phthalate, amyl phthalate or dinoctyl phthalate.
The catalyst system that contains described catalyst component, described catalyst system comprises component i), component ii), preferably by component i), component ii) iii) forms with component;
Component i) be the above-mentioned catalyst component for olefinic polymerization;
Component is ii) organo-aluminium compound;
Component is iii) silicoorganic compound.
The general formula of described organo-aluminium compound is AlRnX
3-nalkylaluminium cpd, in formula, R is the alkyl that hydrogen or carbonatoms are 1-20, X is halogen, the number that n is 1<n≤3; Specifically can be selected from one or more in following compound: triethyl aluminum (AlEt
3), three n-butylaluminum [Al (Bu-n)
3], triisobutyl aluminium [Al (Bu-t)
3], three n-heptyl aluminium, tri-propyl aluminum, tri-n-octylaluminium, triisobutyl aluminium, aluminium diethyl monochloride (AlEt
2cl), a hydrogen diisobutyl aluminum, a chlorine dibutyl aluminium, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, ethyl aluminum dichloride, preferably triethyl aluminum, triisobutyl aluminium.
Described silicoorganic compound are one or more in following compound preferably: Cyclohexylmethyldimethoxysilane (CHMMS), dimethoxydiphenylsilane, dicyclopentyl dimethoxyl silane (DCPMMS), Dicyclohexyldimethoxysilane, cyclopentyl-trimethoxy-silane, tert-butyl trimethoxy silane, 2-ethyl piperidine base Trimethoxy silane, methyl-t-butyldimethoxysilane or 2-ethyl piperidine base tertiary butyl dimethoxy silane.
In above-mentioned ingredient of solid catalyst, the content of described each component is in every mole of magnesium compound, and titanium compound is 0.3 ~ 100 mole, preferably 5 ~ 20 moles; Electron donor compound is 0 ~ 20 mole, preferably 0.02 ~ 0.5 mole.
Beneficial effect of the present invention is:
While using catalyzer of the present invention for propylene polymerization, the degree of isotacticity of catalyst activity and resulting polymers is higher, and catalyst activity decay is slow.
Adopt the compound of compound as shown in general formula I, use it for and prepare olefin polymerization catalyst, form novel catalytic polymerization system, and the catalysis behavior in propylene polymerization is studied to it, the results are shown in subordinate list 1.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
The synthetic detailed introduction of seeing below of particular compound.The compound of general formula I can be used several different methods preparation.Adopt following steps: in corresponding solvent system, the alcohol compound of formula II is reacted with corresponding silane compound, obtain corresponding compound.
General formula I I
Embodiment 1
In a reaction flask; under nitrogen protection and anhydrous condition, add 9,9-dihydroxymethyl fluorenes (5.8 grams), trimethylchlorosilane (6.0 grams) and tetrahydrofuran (THF) (150mL); under cooling conditions, in 2 hours, add sodium hydride (1.2 grams) in batches, add rear room temperature reaction 4 hours.Add saturated aqueous ammonium chloride, after stirring, separate organic phase, use extracted with diethyl ether three times, merge organic phase.Water, saturated nacl aqueous solution washing, remove desolventizing after anhydrous sodium sulfate drying successively.Excess obtains product 9 after column chromatographic isolation and purification, two (trimethylammonium silica methyl) 6.5 grams of the fluorenes (productive rate 70%) of 9-.1H-NMR(δ,ppm,TMS,CDCl
3)：7.25~8.17（8H,m,ArH）,4.23(4H,s,OCH
2)，0.01(18H,m,SiCH
3)。
Embodiment 2
In a reaction flask, under nitrogen protection and anhydrous condition, add 9,9-dihydroxymethyl fluorenes (2.9 grams), triethylamine (11mL) and tetrahydrofuran (THF) (80mL).The mixed solution that was added dropwise to triallyl chlorosilane (5.6 grams) and tetrahydrofuran (THF) (20mL) under cooling conditions in 1 hour, adds rear room temperature reaction 4 hours.Heating reflux reaction 6 hours.React rear cooling, filtered, with ether washing three times, merged organic phase, after anhydrous sodium sulfate drying 24h, removed desolventizing.Excess obtains product 9 after column chromatographic isolation and purification, two (the triallyl silica methyl) fluorenes (3.61 grams (productive rate 42%) of 9-.1H-NMR(δ,ppm,TMS,CDCl
3)：7.20~8.16（8H,m,ArH）,5.73(6H,m,=CH)，5.00(12H,m,=CH
2)，4.32(4H,s,OCH
2)，2.04(12H,m,CH
2)。
Embodiment 3
In a reaction flask; under nitrogen protection and anhydrous condition; add 2-sec.-propyl-2-isopentyl-1; ammediol (9.4 grams), trimethylchlorosilane (11.6 grams) and tetrahydrofuran (THF) (150mL); under cooling conditions, in 2 hours, add sodium hydride (2.4 grams) in batches; add rear room temperature reaction 4 hours, heating reflux reaction 6 hours.After reaction finishes, be down to room temperature, add saturated aqueous ammonium chloride, after stirring, separate organic phase.By extracted with diethyl ether three times, merge organic phase.Water, saturated nacl aqueous solution washing, remove desolventizing after anhydrous sodium sulfate drying successively.Excess obtains product 2-sec.-propyl-2-isopentyl-1 after column chromatographic isolation and purification, two 12.0 grams, (trimethylsiloxy group) propane (productive rate 65%) of 3-.1H-NMR(δ,ppm,TMS,CDCl
3)：3.84(4H,s,OCH
2)，1.84(2H,m,CH)，1.20~1.34(4H,m,CH
2)，0.92~1.16(12H,m,CH
2)，0.01(18H,m,SiCH
3)。
Embodiment 4
In a reaction flask, under nitrogen protection and anhydrous condition, add 2-sec.-propyl-2-isopentyl-1,3-PD (2.5 grams), triethylamine (11mL) and tetrahydrofuran (THF) (80mL).Under cooling conditions, in 1 hour, be added dropwise to triallyl chlorosilane (5.1 grams) and tetrahydrofuran (THF) (20mL), add rear room temperature reaction 4 hours, heating reflux reaction 12 hours.React rear cooling, filtered, with ether washing three times, merged organic phase, after anhydrous sodium sulfate drying spends the night, removed desolventizing.Excess obtains product 2-sec.-propyl-2-isopentyl-1 after column chromatographic isolation and purification, two 2.5 grams, (triallyl siloxy) propane (productive rate 41%) of 3-.1H-NMR(δ,ppm,TMS,CDCl
3)：5.73(6H,m,=CH)，5.00(12H,m,=CH
2)，3.82(4H,s,OCH
2)，1.64~1.98(14H,m,SiCH、CH
2)，1.20~1.34(4H,m,CH
2)，0.92~1.16(6H,m,CH
3)。
Embodiment 5
In a reaction flask that agitator, minim pipette, reflux condensing tube be housed; under nitrogen protection and anhydrous condition; add potassium tert.-butoxide (5.8 grams) and 50 milliliters of tetrahydrofuran (THF)s; under stirring, be added dropwise to 40 milliliters containing 2-allyl group-3-(trimethyl silicane methylene radical of 0.025mol)-1; the tetrahydrofuran solution of 4-butyleneglycol, stirring reaction 4 hours.Cooling lower triallyl chlorosilane (5.1 grams) and the tetrahydrofuran (THF) (20mL) of being slowly added dropwise to of ice-water bath, rises to room temperature reaction 4 hours, heating reflux reaction 12 hours after dripping.After cooling, add dilute hydrochloric acid water and stir 0.5 hour, extracted with diethyl ether 3 times, anhydrous magnesium sulfate drying spends the night.Except after desolventizing, obtain weak yellow liquid, column chromatography separates and obtains product 2-allyl group-3-(trimethyl silicane methylene radical)-Isosorbide-5-Nitrae-bis-(triallyl siloxy) butane (2.3 grams, colourless liquid).1H-NMR(δ,ppm,TMS,CDCl
3)：5.88(7H,m,=CH),4.94~5.15(14H,m,=CH
2),4.09~4.31(4H,m,OCH
2),2.08~2.20(2H,m,CH
2),1.64~1.80（12H,m,CH)），1.35~1.46(2H,m,CH),0.00~0.01(9H,m,SiCH
3)。
The preparation of ingredient of solid catalyst
Embodiment 6
In the reactor of fully replacing through high pure nitrogen, add successively magnesium chloride 4.8g, toluene 95mL, epoxy chloropropane 4ml, tributyl phosphate (TBP) 12.5mL, under stirring, be warming up to 50 ℃, and maintain 2.5 hours, after solid dissolves completely, add Tetra hydro Phthalic anhydride 1.4g, continue to maintain 1 hour, solution is cooled to below-25 ℃, in 1 hour, drip TiCl
4, be slowly warming up to 80 ℃, gradually solids is separated out, add 2,4-dibenzoyl oxygen base pentane (0.006 mole), holding temperature 1 hour, after heat filtering, add toluene 150mL, washing secondary, obtains solid, add toluene 100mL, be warmed up to 110 ℃, carry out three washings, time is respectively 10 minutes, then adds the compound 9 of described structure, two (the triallyl silica methyl) fluorenes (0.006 mole) of 9-, hexane 60mL, stirs 30 minutes, then adds hexane 60mL washed twice.Obtain solids 8.4g(solid ingredient), containing Ti:3.7%, Mg:26.2%, Cl:50.6%.
Embodiment 7
Identical with embodiment 6, just with the compound 9 in embodiment 6, two (the triallyl silica methyl) fluorenes of 9-are changed to 2-sec.-propyl-2-isopentyl-1, two (triallyl siloxy) propane of 3-.
Embodiment 8
Identical with embodiment 6, just with the compound 9 in embodiment 6, two (the triallyl silica methyl) fluorenes of 9-are changed to 2-allyl group-3-(trimethyl silicane methylene radical)-diethyl succinate.
Embodiment 9
Identical with embodiment 6, just, with the compound 2 in embodiment 6,4-dibenzoyl oxygen base pentane is changed to 3-ethyl-2,4-dibenzoyl oxygen base pentane.
Embodiment 10
In the reactor of fully replacing through high pure nitrogen, add successively magnesium chloride 4.8g, toluene 95mL, epoxy chloropropane 4ml, tributyl phosphate (TBP) 12.5mL, under stirring, be warming up to 50 ℃, and maintain 2.5 hours, after solid dissolves completely, add Tetra hydro Phthalic anhydride 1.4g, continue to maintain 1 hour, solution is cooled to below-25 ℃, in 1 hour, drip TiCl
4, slowly be warming up to 80 ℃, gradually solids is separated out, add 2, 4-dibenzoyl oxygen base pentane (0.006 mole), holding temperature 1 hour, after heat filtering, add toluene 150mL, washing secondary, obtain solid, add toluene 100mL, compound 2-sec.-propyl-2-isopentyl-1 that adds again described structure, two (triallyl siloxy) propane (0.006 mole) of 3-, stir 30 minutes, be warmed up to 110 ℃, carry out three washings, time is respectively 10 minutes, add again hexane 60mL washed twice, obtain solids 7.9g(solid ingredient), containing Ti:3.0%, Mg:28.4%, Cl:50.6%.
Embodiment 11
Identical with embodiment 10, just, with the compound 2 in embodiment 10,4-dibenzoyl oxygen base pentane is changed to dibutyl phthalate.
Embodiment 12
In the reactor of fully replacing through high pure nitrogen, add successively magnesium chloride 4.8g, toluene 95mL, epoxy chloropropane 4ml, tributyl phosphate (TBP) 12.5mL, under stirring, be warming up to 50 ℃, and maintain 2.5 hours, after solid dissolves completely, add Tetra hydro Phthalic anhydride 1.4g, continue to maintain 1 hour, solution is cooled to below-25 ℃, in 1 hour, drip TiCl
4slowly be warming up to 80 ℃, gradually solids is separated out, add 2,4-dibenzoyl oxygen base pentane (0.006 mole) and described compound 9, two (the triallyl silica methyl) fluorenes (0.006 mole) of 9-, holding temperature 1 hour, after heat filtering, adds toluene 150mL, washing secondary, obtain solid, add toluene 100mL, stir 30 minutes, be warmed up to 110 ℃, carry out three washings, the time is respectively 10 minutes, then adds hexane 60mL washed twice, obtain solids 7.3g(solid ingredient), containing Ti:3.2%, Mg:25.2%, Cl:50.6%.
Embodiment 13
Identical with embodiment 12, just, with the compound 2 in embodiment, 4-dibenzoyl oxygen base pentane is changed to 3,5-dibenzoyl oxygen base pentane.
Embodiment 14
Identical with embodiment 12, just, with the compound 2 in embodiment, 4-dibenzoyl oxygen base pentane is changed to 9,9-dimethoxy methyl fluorenes.
Embodiment 15
In the reactor of fully replacing through high pure nitrogen, add 400mLTiCl
4, be cooled to-20 ℃, add magnesium ethylate 7.0g, while being warming up to stage by stage 40 ℃ under stirring, add 2,4-dibenzoyl oxygen base pentane (0.006 mole), holding temperature 3 hours, after filtration.Add TiCl
4compound 2-sec.-propyl-2-isopentyl-1 of 100mL and described structure, two (triallyl siloxy) propane (0.006 mole) of 3-, is warmed up to 110 ℃, carries out three times and processes.Add again hexane 60mL washing three times.Obtain solids 6.7g(solid ingredient), containing Ti:3.2%, Mg:23.6%, Cl:48.6%.
Embodiment 16
In the reactor of fully replacing through high pure nitrogen, add 400mLTiCl
4, be cooled to-20 ℃, add magnesium chloride alcohol adduct carrier 7.0g, while being warming up to stage by stage 40 ℃ under stirring, add 2,4-dibenzoyl oxygen base pentane (0.006 mole), holding temperature 2 hours, after filtration.Add TiCl
4compound 2-sec.-propyl-2-isopentyl-1 of 100mL and described structure, two (triallyl siloxy) propane (0.006 mole) of 3-, stirs 1 hour, is warmed up to 110 ℃, carries out three times and processes.Add again hexane 60mL washing three times.Obtain solids 6.3g(solid ingredient), containing Ti:3.3%, Mg:26.8%, Cl:50.6%.
Polymerization examination experiment
Embodiment 17
Volume is the stainless steel cauldron of 5L, after gaseous propylene is fully replaced, adds AlEt32.5mL, and Cyclohexylmethyldimethoxysilane (CHMMS) 5ml makes Al/Si(mol)=25, then the solid ingredient 10mg and the 1.8kg/cm that add above-described embodiment 6 to prepare
2hydrogen, passes into liquid propene 2.5L, is warming up to 70 ℃, maintains this temperature 1 hour, and cooling, bleeds off pressure, and discharging obtains PP resin, active 40600gPP/gCat., the degree of isotacticity 97.6%(of resulting polymers sees attached list 1).
Embodiment 18
With embodiment 17, just by the solid ingredient in the solid ingredient alternative embodiment 17 of synthesized in above-described embodiment 7.Concrete outcome sees attached list 1.
Embodiment 19
With embodiment 17, just by the solid ingredient in the solid ingredient alternative embodiment 17 of synthesized in above-described embodiment 8.Concrete outcome sees attached list 1.
Embodiment 20
With embodiment 17, just by the solid ingredient in the solid ingredient alternative embodiment 17 of synthesized in above-described embodiment 9.Concrete outcome sees attached list 1.
Embodiment 21
With embodiment 17, just by the solid ingredient in the solid ingredient alternative embodiment 17 of synthesized in above-described embodiment 10.Concrete outcome sees attached list 1.
Embodiment 22
With embodiment 17, just by the solid ingredient in the solid ingredient alternative embodiment 17 of synthesized in above-described embodiment 11.Concrete outcome sees attached list 1.
Embodiment 23
With embodiment 17, just by the solid ingredient in the solid ingredient alternative embodiment 17 of synthesized in above-described embodiment 12.Concrete outcome sees attached list 1.
Embodiment 24
With embodiment 17, just by the solid ingredient in the solid ingredient alternative embodiment 17 of synthesized in above-described embodiment 13.Concrete outcome sees attached list 1.
Embodiment 25
With embodiment 17, just by the solid ingredient in the solid ingredient alternative embodiment 17 of synthesized in above-described embodiment 14.Concrete outcome sees attached list 1.
Embodiment 26
With embodiment 17, just by the solid ingredient in the solid ingredient alternative embodiment 17 of synthesized in above-described embodiment 15.Concrete outcome sees attached list 1.
Embodiment 27
With embodiment 17, just by the solid ingredient in the solid ingredient alternative embodiment 17 of synthesized in above-described embodiment 16.Concrete outcome sees attached list 1.
Embodiment 28
With embodiment 17, just polymerization reaction time in embodiment is extended for to 2 hours.Concrete outcome sees attached list 1.
Embodiment 29
With embodiment 17, just polymerization reaction time in embodiment is extended for to 3 hours.Concrete outcome sees attached list 1.
Embodiment 30
With embodiment 23, just polymerization reaction time in embodiment is extended for to 2 hours.Concrete outcome sees attached list 1.
Embodiment 31
With embodiment 23, just polymerization reaction time in embodiment is extended for to 3 hours.Concrete outcome sees attached list 1.
Embodiment 32
With embodiment 24, just polymerization reaction time in embodiment is extended for to 2 hours.Concrete outcome sees attached list 1.
Embodiment 33
With embodiment 24, just polymerization reaction time in embodiment is extended for to 3 hours.Concrete outcome is in Table 1.
Table 1
Claims (15)
1. for a catalyst component for olefinic polymerization, it take magnesium, titanium, halogen and internal electron donor as main component, and described internal electron donor comprises the silane compound as shown in general formula I:
General formula I
R1 in formula, R2, R3, R4 are identical or different, are the alkyl of C1 ~ C20 or the alkyl with vinyl of C2 ~ C20; R5, R6 are identical or different, are the alkyl of C1 ~ C6 or the aralkyl of C6 ~ C20 or alkaryl; A is that one or more replacements or unsubstituted methylene radical, the cycloalkyl of C4 ~ C20 are, the fragrant cyclic group of C5 ~ C20 or condensed ring aromatic base; Integer in n=0 ~ 6.
2. catalyst component according to claim 1, is characterized in that, described silane compound is selected from two (the triallyl silica methyl) fluorenes of one or more in following: 9,9-, 2-sec.-propyl-2-isopentyl-1, two (triallyl siloxy) propane of 3-, 2-allyl group-3-(trimethyl silicane methylene radical)-Isosorbide-5-Nitrae-bis-(triallyl siloxy) butane, 2-propyl group-2-isopentyl-1, two (triallyl siloxy) propane of 3-, 2-allyl group-3-butyl-Isosorbide-5-Nitrae-bis-(triallyl siloxy) butane, 2-propyl group-3-butyl-Isosorbide-5-Nitrae-bis-(triallyl siloxy) butane, 2,3-dibutyl-Isosorbide-5-Nitrae-bis-(triallyl siloxy) butane, 2-ethyl-2-isopentyl-1, two (triallyl siloxy) propane of 3-, 2-sec.-propyl-2-butyl-1, two (triallyl siloxy) propane of 3-, 2,2-dibutyl-1, two (triallyl siloxy) propane of 3-, 3-sec.-propyl-2, two (triallyl siloxy) pentanes of 4-, 3-isopentyl-2, two (triallyl siloxy) pentanes of 4-, 3-methyl-2, two (triallyl siloxy) pentanes of 4-, 3-ethyl-2, two (triallyl siloxy) pentanes of 4-, 3-sec.-propyl-2, two (triallyl siloxy) pentanes of 4-, 3-isopentyl-2, two (triallyl siloxy) pentanes of 4-, 3-butyl-2, two (triallyl siloxy) pentanes of 4-, 3-Bian Ji-2, two (triallyl siloxy) pentanes of 4-, 1,3-phenylbenzene-1, two (triallyl siloxy) propane of 3-, 1,3-phenylbenzene-2-ethyl-1, two (triallyl siloxy) propane of 3-, 1,3-phenylbenzene-2-isopentyl-1, two (triallyl siloxy) propane of 3-, 1,3-phenylbenzene-2-butyl-1, two (triallyl siloxy) propane of 3-, 1-methyl-2-butyl-3-phenyl-1, two (triallyl siloxy) propane of 3-, 1-methyl-3-phenyl-1, two (triallyl siloxy) propane of 3-, 1,2-dimethyl-3-phenyl-1, two (triallyl siloxy) propane of 3-, 1-methyl-2-sec.-propyl-3-phenyl-1, two (triallyl siloxy) propane of 3-, 1-methyl-3-phenyl-1, two (triallyl siloxy) propane of 3-, two (triallyl siloxy) propane of 1-methyl-2-ethyl-3-phenyl-1 and 3-.
3. catalyst component according to claim 1 and 2, it is characterized in that, described internal electron donor also comprises one or more in following compound: diatomic alcohol acid ester cpds, diether compound, dibasic aliphatic carboxylic acid ester compound and aromatic polycarboxylic acid esters compound.
4. catalyst component according to claim 3, it is characterized in that, described diatomic alcohol acid ester cpds is one or more in following compound preferably: 2, 4-dibenzoyl oxygen base pentane, 3-methyl-2, 4-dibenzoyl oxygen base pentane, 3-ethyl-2, 4-dibenzoyl oxygen base pentane, 3, 5-dibenzoyl oxygen base heptane, 4-ethyl-3, 5-dibenzoyl oxygen base heptane, 3-propyl group-1, 2-bis-(2-isopropyl benzene methanoyl) benzene, 3-methyl isophthalic acid, 2-bis-(2-isopropyl benzene methanoyl) benzene, 3-sec.-propyl-1, 2-dibenzoyl oxygen base benzene, 9, 9 '-dibenzoyl oxygen methyl fluorenes, 2-sec.-propyl-2-isopentyl-1, 3-dibenzoyl oxygen base propane, 4-methyl-3, 5-dibenzoyl oxygen base heptane or 4-sec.-propyl-3, 5-dibenzoyl oxygen base heptane.
5. catalyst component according to claim 3, it is characterized in that, described diether compound is one or more in following compound preferably: 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isobutyl--1,3-Propanal dimethyl acetal or 9,9-dimethoxy methyl fluorenes.
6. catalyst component according to claim 3, it is characterized in that, described dibasic aliphatic carboxylic acid ester compound is one or more in following compound preferably: dibutyl succinate, 2-diethyl butylmalonate, ethyl glutarate or pentanedioic acid dibutylester.
7. catalyst component according to claim 3, it is characterized in that, described aromatic polycarboxylic acid esters compound is selected from one or more in following compound: n-butyl phthalate, diethyl phthalate, diisobutyl phthalate, 3-methyl-dibutyl phthalate, amyl phthalate or dinoctyl phthalate.
8. according to a preparation method for the catalyst component described in any one in claim 1-7, comprise the following steps:
A) magnesium halide is dissolved in to organic epoxy compounds and organo phosphorous compounds and makes homogeneous solution, in solvent system, add or do not add inert diluent; Inert diluent is preferably non-polar solvent, more preferably toluene;
B) above-mentioned homogeneous solution is mixed with titanium tetrahalide or derivatives thereof, add precipitation additive in reaction system, solids is separated out;
C) internal electron donor is attached on solids, then processes with titanium tetrahalide or inert diluent, then with the silane compound shown in general formula I, process, obtain comprising the solid catalyst of titanium, magnesium, halogen and internal electron donor.
9. preparation method according to claim 8, it is characterized in that, step a) described in organo phosphorous compounds be that phosphate compounds is one or more the mixture in tributyl phosphate, three iso-butyl ester of phosphoric acid, tricresyl phosphate fourth monooctyl ester, triethyl phosphate or TNPP tri n pentyl phosphate.
10. preparation method according to claim 8, is characterized in that, step b) described in precipitation additive be selected from one or more in following compound: organic acid anhydride, organic acid, ether, ketone, ether, diol-lipid; The wherein preferred diacetyl oxide of organic dianhydride, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE or pyromellitic acid anhydride; The preferred acetic acid of organic acid, propionic acid, butyric acid, acrylic or methacrylic acid; The preferred acetone of ketone, methylethylketone or benzophenone; The preferred methyl ether of ether, ether, propyl ether, butyl ether or amyl ether; Diol-lipid preferably 2,4-dibenzoyl oxygen base pentane, 3-ethyl-2,4-dibenzoyl oxygen base pentane, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal or 9,9-dimethoxy methyl fluorenes.
11. 1 kinds according to the preparation method of the catalyst component described in any one in claim 1-7, comprise the following steps: by magnesium halide or organo-magnesium compound, alcohol compound and titanate ester or halogenated titanium compound abundant mix and blend in inert solvent, heating is cooling afterwards to be obtained ball-type carrier or add inert solvent to obtain uniform alcohol adduct solution; Above-mentioned carrier or homogeneous solution are mixed with titanium tetrahalide or derivatives thereof, in temperature, it is-80～0 ℃, at preferably-40～-10 ℃, maintaining for some time post-heating heats up, add internal electron donor, with titanium tetrahalide or inert diluent, process again, then use the compound treatment of general formula I, finally by the solid catalyst that obtains comprising the compositions such as titanium, magnesium, halogen, electron donor after filtering, wash, being dried; The preferred toluene of wherein said inert solvent.
Preparation method in 12. according to Claim 8-11 described in any one, is characterized in that, in described ingredient of solid catalyst, by every mole of magnesium compound, titanium compound is 0.3 ~ 100 mole, preferably 5 ~ 20 moles; Internal electron donor compound is 0 ~ 15 mole, preferably 0.01 ~ 0.5 mole.
13. 1 kinds of catalyst system containing the catalyst component described in any one in good grounds claim 1-7, described catalyst system comprises component i), component ii), preferably by component i), component ii) iii) forms with component, wherein, component i) be described catalyst component, component is ii) organo-aluminium compound, and component is iii) silicoorganic compound.
14. catalyst system according to claim 13, is characterized in that, the general formula that described organo-aluminium compound is described organo-aluminium compound is AlR
nx
3-nalkylaluminium cpd, in formula, R is the alkyl that hydrogen or carbonatoms are 1-20, X is halogen, the number that n is 1<n≤3; Preferred one or more in the following compound: triethyl aluminum, three n-butylaluminum, triisobutyl aluminium, three n-heptyl aluminium, tri-propyl aluminum, tri-n-octylaluminium, triisobutyl aluminium, aluminium diethyl monochloride, a hydrogen diisobutyl aluminum, a chlorine dibutyl aluminium, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride or ethyl aluminum dichloride; More preferably triethyl aluminum and/or triisobutyl aluminium.
15. catalyst system according to claim 13, it is characterized in that, described silicoorganic compound are selected from one or more in lower compound: Cyclohexylmethyldimethoxysilane, dimethoxydiphenylsilane, dicyclopentyl dimethoxyl silane (DCPMMS), Dicyclohexyldimethoxysilane, cyclopentyl-trimethoxy-silane, tert-butyl trimethoxy silane, 2-ethyl piperidine base Trimethoxy silane, methyl-t-butyldimethoxysilane or 2-ethyl piperidine base tertiary butyl dimethoxy silane.
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