CN103665201B - A kind of catalytic component for olefinic polymerization and preparation method thereof and catalyst system and catalyzing - Google Patents
A kind of catalytic component for olefinic polymerization and preparation method thereof and catalyst system and catalyzing Download PDFInfo
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Abstract
The present invention relates to a kind of catalytic component for olefinic polymerization and preparation method thereof and catalyst system and catalyzing.In catalyst preparation process, add a kind of silane compound, form catalytic polymerization system.This catalyst has higher activity and capacity of orientation, the feature that decay of activity is slower.
Description
Technical field
The present invention relates to manufacture of polyolefins technical field.It is more particularly related to the catalysis of a kind of olefinic polymerization
Agent and preparation method thereof and catalyst system and catalyzing.
Background technology
Since the fifties, the research and development of propylene polymerization catalyst are from the TiCl of the first generation3AlCl3/AlEt2Cl body
System and the TiCl of the second filial generation3/AlEt2Cl system, the magnesium chloride to the third generation be carrier, monoesters or aromatic dibasic acid ester be interior giving
Electron, silane are the TiCl of external electron donor4·ED·MgCl2/AlR3ED system, the catalytic polymerization of catalyst is lived
Property and gained polypropylene isotacticity height are all greatly improved.In the prior art, for the titanium catalyst of propylene polymerization
System is many using magnesium, titanium, halogen and electron donor as basis, and wherein electron donor compound is must not in catalytic component
One of composition that can lack.With the development of electron donor compound, polyolefin catalyst is continuously updated the replacement the most therewith.
At present, it has been disclosed that multiple electron donor compound, such as monocarboxylic esters or multi-carboxylate, anhydride, ketone, list
Ether or polyether, alcohol, amine etc. and derivant thereof, the most conventional is aromatic dicarboxylic acids's esters, such as phthalic acid two
N-butyl or diisobutyl phthalate etc., can be found in United States Patent (USP) US4784983.United States Patent (USP) US4971937 and Europe
In the component for olefin polymerization catalyst disclosed in patent EP0728769, it is special containing two ethers to have employed
The 1 of group, 3-diether compound is electron donor, and such as 2-isopropyl-2-isopentyl-1,3-dimethoxy propane, 2,2-bis-is different
Butyl-1,3-dimethoxy propane and 9,9-bis-(methoxyl methyl) fluorenes etc..Disclose the most again the dibasic aliphatic that a class is special
Carboxylic acid ester compound, (sees WO98/56830, WO98/56834, WO01/ such as succinate, malonate, glutarate etc.
57099, WO01/63231 and WO00/55215), the use of this kind of electron donor compound not only can improve the activity of catalyst,
And the molecular weight distribution of gained acrylic polymers is substantially widened.
But, above-mentioned employing binary aromatic carboxylic acid's ester type compound disclosed above, containing the 1 of two ether groups, 3-bis-
Catalyst for olefinic polymerization prepared by ether compound and dibasic aliphatic carboxylic acid ester compound is the most all
There is certain defect, the catalysis activity for example with the catalyst of aromatic dicarboxylic acids's ester type compound is relatively low, Er Qiesuo
The molecular weight distribution obtaining polymer is the narrowest；Use 1, although the catalyst activity of 3-diether compound is higher, and catalyst
To the sensitivity that hydrogen is adjusted, but the narrow molecular weight distribution of resulting polymers, it is unfavorable for the exploitation of the polymer difference trade mark；And adopt
Catalysis activity with the catalyst of the disclosedest dibasic aliphatic carboxylate is the most on the low side, and is not using external electron donor group
Timesharing, the isotacticity of resulting polymers is relatively low, and hydrogen response is the most poor.The decay of activity of catalyst is very fast simultaneously, is unfavorable for
The long period application of catalyst.
In prior art, although disclose substantial amounts of silane compound, such as: Chinese patent 1939939A reports with alkane
TMOS compound is the manufacture method of the acrylic polymers of external electron donor, containing three in the molecular structure of this compounds
Individual alkoxyl, typical compound includes 1,1,1-trimethyl-3,3,3-triethoxies two silicon propane (TMTEDSP), 1,1,1-
Trimethyl-4,4,4-triethoxies two silicon propane (TMTEDSB), 1,1,1-trimethyl-5,5,5-triethoxy two silicon propane
(TMTEDSPN), 1,1,1-trimethyl-3,3,3-trimethoxies two silicon propane (TMTMDSP) etc., available high laws, Gao Rong
The acrylic polymers of body flow index.WO00/63261 discloses the class silanes external electron donor chemical combination for olefinic polymerization
Thing, formula is R1aR2b(OR3)c, wherein c be 1 ~ 3 integer and (a+b+c) be 4, its preferred external electron donor includes hexamethylene
Ylmethyl dimethoxysilane (CHMMS) and cyclohexyl trimethoxy silane etc., when propylene polymerization, available high
The polymeric articles of normality.
But these silane compounds are mostly used as external electron donor, be applied at present catalyst preparation and as interior to
Research report in terms of electron is less.
Toho(east nation titanium) company disclosed a kind of silanes chemical combination in its patent JP20050250579 in 2005
Thing, finds the feature through the magnesium alcohol catalyst of these compound treatment with long-acting catalysis activity, the decay of activity of catalyst
Relatively slow, but preparation technology is cumbersome, needs first to prepare catalyst, uses compound treatment the most again.
Summary of the invention
It is an object of the invention to as solving the problems referred to above, the present invention provides a kind of catalyst for olefinic polymerization, special
It it not the catalyst of propylene polymerization.Class silanes chemical combination as shown in following formula I is added in catalyst preparation process
Thing, forms novel catalytic polymerization system.This catalyst has higher activity and capacity of orientation, and decay of activity is slower
Feature.
The technical scheme is that
A kind of catalytic component for olefinic polymerization, it is with magnesium, titanium, halogen and internal electron donor as main component, institute
The internal electron donor stated includes the silane compound as shown in formula I,
Formula I
R1, R2, R3, R4 in formula are identical or different, for alkyl or the alkyl with vinyl of C2 ~ C20 of C1 ~ C20；
R5, R6 are identical or different, for the alkyl of C1 ~ C6 or the aralkyl of C6 ~ C20 or alkaryl；A is one or more replacement or does not takes
The methylene in generation, the cycloalkyl of C4 ~ C20, the fragrant ring group of C5 ~ C20 or polycyclic aromatic base；Integer in n=0 ~ 6.
One or more in following compound of given silane compound: 9,9-double (triallyl silica
Methyl) fluorenes, 2-isopropyl-2-isopentyl-1,3-double (triallyl siloxy) propane, 2-pi-allyl-3-(trimethyl silicane methylene
Base)-Isosorbide-5-Nitrae-two (triallyl siloxy) butane, 2-propyl group-2-isopentyl-1,3-double (triallyl siloxy) propane, 2-
Pi-allyl-3-butyl-Isosorbide-5-Nitrae-two (triallyl siloxy) butane, 2-propyl group-3-butyl-Isosorbide-5-Nitrae-two (triallyl siloxy)
Butane, 2,3-dibutyl-Isosorbide-5-Nitrae-two (triallyl siloxy) butane, 2-ethyl-2-isopentyl-1, double (the triallyl silicon of 3-
Epoxide) propane, 2-isopropyl-2-butyl-1, double (triallyl siloxy) propane of 3-, 2,2-dibutyl-1, double (three allyls of 3-
Base siloxy) propane, 3-isopropyl-2,4-double (triallyl siloxy) pentane, 3-isopentyl-2, double (the triallyl silicon of 4-
Epoxide) pentane, 3-methyl-2,4-double (triallyl siloxy) pentane, 3-ethyl-2, double (the triallyl siloxy) penta of 4-
Alkane, 3-isopropyl-2,4-double (triallyl siloxy) pentane, 3-isopentyl-2,4-double (triallyl siloxy) pentane, 3-
Butyl-2,4-double (triallyl siloxy) pentane, 3-benzyl group-2, double (triallyl siloxy) pentane of 4-, 1,3-diphenyl-
1,3-double (triallyl siloxy) propane, 1,3-diphenyl-2-ethyl-1, double (triallyl siloxy) propane of 3-, 1,3-
Diphenyl-2-isopentyl-1, double (triallyl siloxy) propane of 3-, 1,3-diphenyl-2-butyl-1, the double (triallyl of 3-
Siloxy) propane, 1-methyl-2-butyl-3-phenyl-1,3-double (triallyl siloxy) propane, 1-methyl-3-phenyl-1,
Double (triallyl siloxy) propane of 3-, 1,2-dimethyl-3-phenyl-1, double (triallyl siloxy) propane of 3-, 1-methyl-
2-isopropyl-3-phenyl-1,3-double (triallyl siloxy) propane, 1-methyl-3-phenyl-1, double (the triallyl silica of 3-
Base) propane, double (triallyl siloxy) propane of 1-methyl-2-ethyl-3-phenyl-1 and 3-.
Described internal electron donor also includes one or more in following compound: diatomic alcohol acid ester compounds, diether
Compounds, dibasic aliphatic carboxylic acid ester compound and aromatic polycarboxylic acid esters compound.
Described diatomic alcohol acid ester compounds preferably is selected from one or more in following compound: 2,4-dibenzoyl epoxides penta
Alkane, 3-methyl-2,4-dibenzoyl epoxide pentane, 3-ethyl-2,4-dibenzoyl epoxide pentane, 3,5-dibenzoyl epoxide heptan
Alkane, 4-ethyl-3,5-dibenzoyl epoxide heptane, 3-propyl group-1,2-bis-(2-diisopropylbenzoyl peroxide epoxide) benzene, 3-methyl isophthalic acid,
2-bis-(2-diisopropylbenzoyl peroxide epoxide) benzene, 3-isopropyl-1,2-dibenzoyl epoxide benzene, 9,9 '-dibenzoyl oxygen methyl fluorenes,
2-isopropyl-2-isopentyl-1,3-dibenzoyl epoxide propane, 4-methyl-3,5-dibenzoyl epoxide heptane or 4-isopropyl-
3,5-dibenzoyl epoxide heptane.
One or more in following compound of described diether compound: 2-isopropyl-2-isopentyl-1,3-bis-
Methoxy propane, 2-isopropyl-2-isobutyl group-1,3-dimethoxy propane or 9,9-dimethoxy methyl fluorenes.
One or more in following compound of described dibasic aliphatic carboxylic acid ester compound: succinic acid two fourth
Ester, 2-diethyl butylmalonate, ethyl glutarate or dibutyl glutarate.
One or more in following compound of described aromatic polycarboxylic acid esters compound: the positive fourth of phthalic acid two
Ester, diethyl phthalate, diisobutyl phthalate, 3-methyl-dibutyl phthalate, phthalic acid two are just
Pentyl ester or dinoctyl phthalate.
Above-mentioned catalyst component can use following two method to prepare:
Method one:
A) magnesium halide is dissolved in organic epoxy compound thing and organic phosphorus compound makes homogeneous solution, add in dicyandiamide solution
Enter or be added without inert diluent；Inert diluent is preferably non-polar solven, more preferably toluene；
B) above-mentioned homogeneous solution titanium tetrahalide or derivatives thereof is mixed, reaction system adds precipitation additive, solid
Thing separates out；
C) internal electron donor is attached on solids, then processes, then with above-mentioned with titanium tetrahalide or inert diluent
Silane compound shown in formula I processes, and obtains including the solid catalyst of titanium, magnesium, halogen and internal electron donor.
Organic phosphorus compound described in step a) be phosphate compounds be tributyl phosphate, three iso-butyl ester of phosphoric acid, phosphorus
The mixture of one or more in acid three fourth monooctyl esters, triethyl phosphate or TNPP tri n pentyl phosphate.
One or more in the following compound of precipitation additive described in step b): organic acid anhydride, organic acid, ether,
Ketone, diol ester, ethers.The preferred acetic anhydride of organic dianhydride, phthalic anhydride, succinic anhydride, maleic anhydride or equal benzene tetramethyl
Acid dianhydride；The acid of the preferred acetic acid of organic acid, propanoic acid, butanoic acid, acrylic or methacrylic；The preferred acetone of ketone, butanone or benzophenone；
The preferred methyl ether of ether, ether, propyl ether, butyl ether or amyl ether；Diol ester preferably 2,4-dibenzoyl epoxide pentane, 3-ethyl-2,4-bis-
Benzoyloxy pentane, 2-isopropyl-2-isopentyl-1,3-dimethoxy propane or 9,9-dimethoxy methyl fluorenes.
The described internal electron donor of step c) is selected from the mixing of one or more of following compound: the silanes of the present invention
Compound, diatomic alcohol acid ester compounds, diether compound and dibasic aliphatic carboxylic acid ester compound and aromatic polycarboxylic acid esters
Compounds.
Described diatomic alcohol acid ester compounds preferably is selected from one or more in following compound: 2,4-dibenzoyl epoxides penta
Alkane, 3-methyl-2,4-dibenzoyl epoxide pentane, 3-ethyl-2,4-dibenzoyl epoxide pentane, 3,5-dibenzoyl epoxide heptan
Alkane, 4-ethyl-3,5-dibenzoyl epoxide heptane, 3-propyl group-1,2-bis-(2-diisopropylbenzoyl peroxide epoxide) benzene, 3-methyl isophthalic acid,
2-bis-(2-diisopropylbenzoyl peroxide epoxide) benzene, 3-isopropyl-1,2-dibenzoyl epoxide benzene, 9,9 '-dibenzoyl oxygen methyl fluorenes,
2-isopropyl-2-isopentyl-1,3-dibenzoyl epoxide propane, 4-methyl-3,5-dibenzoyl epoxide heptane or 4-isopropyl-
3,5-dibenzoyl epoxide heptane；
One or more in following compound of described diether compound: 2-isopropyl-2-isopentyl-1,3-bis-
Methoxy propane, 2-isopropyl-2-isobutyl group-1,3-dimethoxy propane or 9,9-dimethoxy methyl fluorenes.
One or more in following compound of described dibasic aliphatic carboxylic acid ester compound: succinic acid two fourth
Ester, 2-diethyl butylmalonate, ethyl glutarate or dibutyl glutarate.
One or more in following compound of described aromatic polycarboxylic acid esters compound: the positive fourth of phthalic acid two
Ester, diethyl phthalate, diisobutyl phthalate, 3-methyl-dibutyl phthalate, phthalic acid two are just
Pentyl ester or dinoctyl phthalate.
Method two:
By magnesium halide or organo-magnesium compound, alcohol compound and titanate ester or halogenated titanium compound in atent solvent
Being sufficiently mixed stirring, after heating, cooling obtains ball-type carrier or addition atent solvent obtains uniform alcohol adduct solution.By above-mentioned
Carrier or homogeneous solution mix with titanium tetrahalide or derivatives thereof, are-80～0 DEG C in temperature, preferably-40～-10 DEG C at maintain
A period of time post-heating heats up, and adds internal electron donor, then processes with titanium tetrahalide or inert diluent, then with formula I's
Compound treatment, eventually passes filtration, washing, obtains after drying including that the solid of the compositions such as titanium, magnesium, halogen, electron donor is urged
Agent.
The preferred toluene of atent solvent described in method two, described internal electron donor is selected from one or more of following compound
Mixing: the silane compound of the present invention, diatomic alcohol acid ester compounds, diether compound and dibasic aliphatic carboxylic acid esters
Compound and aromatic polycarboxylic acid esters compound.
Described diatomic alcohol acid ester compounds preferably is selected from one or more in following compound: 2,4-dibenzoyl epoxides penta
Alkane, 3-methyl-2,4-dibenzoyl epoxide pentane, 3-ethyl-2,4-dibenzoyl epoxide pentane, 3,5-dibenzoyl epoxide heptan
Alkane, 4-ethyl-3,5-dibenzoyl epoxide heptane, 3-propyl group-1,2-bis-(2-diisopropylbenzoyl peroxide epoxide) benzene, 3-methyl isophthalic acid,
2-bis-(2-diisopropylbenzoyl peroxide epoxide) benzene, 3-isopropyl-1,2-dibenzoyl epoxide benzene, 9,9 '-dibenzoyl oxygen methyl fluorenes,
2-isopropyl-2-isopentyl-1,3-dibenzoyl epoxide propane, 4-methyl-3,5-dibenzoyl epoxide heptane or 4-isopropyl-
3,5-dibenzoyl epoxide heptane.
One or more in following compound of described diether compound: 2-isopropyl-2-isopentyl-1,3-bis-
Methoxy propane, 2-isopropyl-2-isobutyl group-1,3-dimethoxy propane or 9,9-dimethoxy methyl fluorenes.
One or more in following compound of described dibasic aliphatic carboxylic acid ester compound: succinic acid two fourth
Ester, 2-diethyl butylmalonate, ethyl glutarate or dibutyl glutarate.
One or more in following compound of described aromatic polycarboxylic acid esters compound: the positive fourth of phthalic acid two
Ester, diethyl phthalate, diisobutyl phthalate, 3-methyl-dibutyl phthalate, phthalic acid two are just
Pentyl ester or dinoctyl phthalate.
Containing the catalyst system and catalyzing of described catalytic component, described catalyst system and catalyzing comprises component i), component ii), preferably by group
Part i), component ii) iii) forms with component；
Component i) is the above-mentioned catalytic component for olefinic polymerization；
Component is ii) organo-aluminum compound；
Component is iii) organo-silicon compound.
The formula of described organo-aluminum compound is AlRnX3-nAlkyl aluminum compound, in formula, R is hydrogen or carbon number is 1-
The alkyl of 20, X is halogen, and n is the number of 1 < n≤3；Specifically it is selected from one or more in following compound: triethyl aluminum
(AlEt3), three n-butylaluminum [Al (Bu-n)3], triisobutyl aluminium [Al (Bu-t)3], three n-heptyl aluminum, tri-propyl aluminum, three the most pungent
Base aluminum, triisobutyl aluminium, aluminium diethyl monochloride (AlEt2Cl), a hydrogen diisobutyl aluminum, a chlorine dibutyl aluminum, chlorine two isobutyl
Base aluminum, sesquialter ethylmercury chloride aluminum, ethyl aluminum dichloride, preferably triethyl aluminum, triisobutyl aluminium.
Described organo-silicon compound preferably are selected from one or more in following compound: Cyclohexylmethyldimethoxysilane
(CHMMS), dimethoxydiphenylsilane, dicyclopentyl dimethoxyl silane (DCPMMS), Dicyclohexyldimethoxysilane,
Cyclopentyl-trimethoxy-silane, tert-butyl trimethoxy silane, 2-ethyl piperidine base trimethoxy silane, methyl tertbutyl diformazan
TMOS or 2-ethyl piperidine base t-butyldimethoxysilane.
In above-mentioned ingredient of solid catalyst, the content of described each component is in terms of 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.
Present invention have the beneficial effect that
Use catalyst of the present invention when propylene polymerization, catalyst activity and the isotactic of resulting polymers
Spending higher, catalyst activity decay is slow.
Use compound compound as shown in formula I, use it for preparing olefin polymerization catalyst, constitute novel
Catalytic polymerization system, and its catalysis behavior in propylene polymerization is studied, result sees attached list 1.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.
What the synthesis of particular compound saw below is discussed in detail.Compounds of formula I can use multiple method to prepare.Use
Following steps: in corresponding dicyandiamide solution, react the alcohol compound of Formula II with corresponding silane compound, obtain
Corresponding compound.
Formula II
Embodiment 1
In a reaction bulb, under nitrogen protection and anhydrous condition, add 9,9-dihydroxymethyl fluorenes (5.8 grams), trimethyl
Chlorosilane (6.0 grams) and oxolane (150mL), be dividedly in some parts sodium hydride (1.2 grams) in 2 hours, add under cooling condition
Rear room temperature reaction 4 hours.Add saturated aqueous ammonium chloride, after stirring, separate organic facies, extract three times with ether, merge organic
Phase.Successively with water, saturated nacl aqueous solution washing, anhydrous sodium sulfate removes solvent after drying.Excess is through column chromatographic isolation and purification
After obtain product 9, double (the trimethyl silica methyl) fluorenes 6.5 grams (productivity 70%) of 9-.1H-NMR(δ,ppm,TMS,CDCl3): 7.25
~ 8.17(8H, m, ArH), 4.23 (4H, s, OCH2), 0.01 (18H, m, SiCH3)。
Embodiment 2
In a reaction bulb, under nitrogen protection and anhydrous condition, addition 9,9-dihydroxymethyl fluorenes (2.9 grams), triethylamine
(11mL) with oxolane (80mL).In 1 hour, triallyl chlorosilane (5.6 grams) and tetrahydrochysene furan it is added dropwise under cooling condition
Mutter the mixed liquor of (20mL), add rear room temperature reaction 4 hours.Heating reflux reaction 6 hours.Lower the temperature after having reacted, filter, use
Ether washs three times, merges organic facies, and anhydrous sodium sulfate removes solvent after being dried 24h.Excess obtains after column chromatographic isolation and purification
To product 9, double (the triallyl silica methyl) fluorenes (3.61 grams (productivity 42%) of 9-.1H-NMR(δ,ppm,TMS,CDCl3): 7.20
~ 8.16(8H, m, ArH), 5.73 (6H, m ,=CH), 5.00 (12H, m ,=CH2), 4.32 (4H, s, OCH2), 2.04 (12H, m,
CH2)。
Embodiment 3
In a reaction bulb, under nitrogen protection and anhydrous condition, add 2-isopropyl-2-isopentyl-1,3-PD
(9.4 grams), trim,ethylchlorosilane (11.6 grams) and oxolane (150mL), be dividedly in some parts hydrogenation under cooling condition in 2 hours
Sodium (2.4 grams), adds rear room temperature reaction 4 hours, heating reflux reaction 6 hours.Reaction is down to room temperature after terminating, and adds saturated chlorination
Aqueous ammonium, separates organic facies after stirring.Extract three times with ether, merge organic facies.Wash with water, saturated nacl aqueous solution successively
Washing, anhydrous sodium sulfate removes solvent after drying.Excess obtain after column chromatographic isolation and purification product 2-isopropyl-2-isopentyl-
1,3-double 12.0 grams of (trimethylsiloxy group) propane (productivity 65%).1H-NMR(δ,ppm,TMS,CDCl3): 3.84 (4H, s,
OCH2), 1.84 (2H, m, CH), 1.20 ~ 1.34 (4H, m, CH2), 0.92 ~ 1.16 (12H, m, CH2), 0.01 (18H, m,
SiCH3)。
Embodiment 4
In a reaction bulb, under nitrogen protection and anhydrous condition, add 2-isopropyl-2-isopentyl-1,3-PD
(2.5 grams), triethylamine (11mL) and oxolane (80mL).In 1 hour, triallyl chlorosilane it is added dropwise under cooling condition
(5.1 grams) and oxolane (20mL), add rear room temperature reaction 4 hours, heating reflux reaction 12 hours.Drop after having reacted
Temperature, filters, and washs three times with ether, merges organic facies, and anhydrous sodium sulfate removes solvent after being dried overnight.Excess divides through column chromatography
From obtaining product 2-isopropyl-2-isopentyl-1 after purification, double 2.5 grams of (triallyl siloxy) propane (productivity 41%) of 3-.
1H-NMR(δ,ppm,TMS,CDCl3): 5.73 (6H, m ,=CH), 5.00 (12H, m ,=CH2), 3.82 (4H, s, OCH2), 1.64 ~
1.98(14H,m,SiCH、CH2), 1.20 ~ 1.34 (4H, m, CH2), 0.92 ~ 1.16 (6H, m, CH3)。
Embodiment 5
One equipped with agitator, minim pipette, reflux condensing tube reaction bulb in, nitrogen protection and anhydrous condition under, add
Enter potassium tert-butoxide (5.8 grams) and 50 milliliters of oxolanes, under stirring, be added dropwise to 40 milliliters of 2-pi-allyl-3-containing 0.025mol
The tetrahydrofuran solution of (trimethyl silicane methylene)-BDO, stirring reaction 4 hours.It is slowly added dropwise under ice-water bath cooling
Enter triallyl chlorosilane (5.1 grams) and oxolane (20mL), after dripping, be warmed to room temperature reaction 4 hours, be heated to reflux anti-
Answer 12 hours.After cooling, adding dilute hydrochloric acid water and stir 0.5 hour, ether extracts 3 times, and anhydrous magnesium sulfate is dried overnight.Remove solvent
After obtain weak yellow liquid, column chromatography separates and obtains product 2-pi-allyl-3-(trimethyl silicane methylene)-Isosorbide-5-Nitrae-two (three allyls
Base siloxy) butane (2.3 grams, colourless liquid).1H-NMR(δ,ppm,TMS,CDCl3): 5.88 (7H, m ,=CH), 4.94 ~
5.15(14H,m,=CH2),4.09~4.31(4H,m,OCH2),2.08~2.20(2H,m,CH2), 1.64 ~ 1.80(12H, m,
CH)), 1.35 ~ 1.46 (2H, m, CH), 0.00 ~ 0.01 (9H, m, SiCH3)。
The preparation of ingredient of solid catalyst
Embodiment 6
In the reactor being sufficiently displaced from through high pure nitrogen, it is sequentially added into magnesium chloride 4.8g, toluene 95mL, epoxy chloropropionate
Alkane 4ml, tributyl phosphate (TBP) 12.5mL, be warming up to 50 DEG C under stirring, and maintains 2.5 hours, after solid is completely dissolved,
Add phthalic anhydride 1.4g, continue to 1 hour, solution is cooled to less than-25 DEG C, in 1 hour, drip TiCl4, slow
Slowly it is warming up to 80 DEG C, gradually solids is separated out, add 2,4-dibenzoyl epoxide pentane (0.006 mole), maintain temperature 1 little
Time, after heat filtering, add toluene 150mL, wash secondary, obtain solid, add toluene 100mL, be warmed up to 110 DEG C, carry out three
Secondary washing, the time is respectively 10 minutes, adds the compound 9 of described structure, double (the triallyl silica methyl) fluorenes (0.006 of 9-
Mole), hexane 60mL, stirs 30 minutes, adds hexane 60mL and wash twice.Obtain solids 8.4g(solid constituent), contain
Ti:3.7%, Mg:26.2%, Cl:50.6%.
Embodiment 7
Same as in Example 6, simply with the compound 9 in embodiment 6, double (the triallyl silica methyl) fluorenes of 9-is changed to 2-
Isopropyl-2-isopentyl-1, double (triallyl siloxy) propane of 3-.
Embodiment 8
Same as in Example 6, simply with the compound 9 in embodiment 6, double (the triallyl silica methyl) fluorenes of 9-is changed to 2-
Pi-allyl-3-(trimethyl silicane methylene)-diethyl succinate.
Embodiment 9
Same as in Example 6, simply with the compound 2 in embodiment 6,4-dibenzoyl epoxide pentane be changed to 3-ethyl-
2,4-dibenzoyl epoxide pentanes.
Embodiment 10
In the reactor being sufficiently displaced from through high pure nitrogen, it is sequentially added into magnesium chloride 4.8g, toluene 95mL, epoxy chloropropionate
Alkane 4ml, tributyl phosphate (TBP) 12.5mL, be warming up to 50 DEG C under stirring, and maintains 2.5 hours, after solid is completely dissolved,
Add phthalic anhydride 1.4g, continue to 1 hour, solution is cooled to less than-25 DEG C, in 1 hour, drip TiCl4, slow
Slowly it is warming up to 80 DEG C, gradually solids is separated out, add 2,4-dibenzoyl epoxide pentane (0.006 mole), maintain temperature 1 little
Time, after heat filtering, add toluene 150mL, wash secondary, obtain solid, add toluene 100mL, add the change of described structure
Compound 2-isopropyl-2-isopentyl-1, double (triallyl siloxy) propane (0.006 mole) of 3-, stirs 30 minutes, is warmed up to
110 DEG C, carrying out three washings, the time is respectively 10 minutes, adds hexane 60mL and washes twice, and obtains solids 7.9g(solid
Component), containing Ti:3.0%, Mg:28.4%, Cl:50.6%.
Embodiment 11
Same as in Example 10, simply with the compound 2 in embodiment 10,4-dibenzoyl epoxide pentane is changed to adjacent benzene two
Formic acid dibutyl ester.
Embodiment 12
In the reactor being sufficiently displaced from through high pure nitrogen, it is sequentially added into magnesium chloride 4.8g, toluene 95mL, epoxy chloropropionate
Alkane 4ml, tributyl phosphate (TBP) 12.5mL, be warming up to 50 DEG C under stirring, and maintains 2.5 hours, after solid is completely dissolved,
Add phthalic anhydride 1.4g, continue to 1 hour, solution is cooled to less than-25 DEG C, in 1 hour, drip TiCl4, slow
Slowly it is warming up to 80 DEG C, gradually solids is separated out, add 2,4-dibenzoyl epoxide pentane (0.006 mole) and described compound
9,9-double (triallyl silica methyl) fluorenes (0.006 mole), maintain temperature 1 hour, after heat filtering, add toluene 150mL, wash
Washing secondary, obtain solid, add toluene 100mL, stir 30 minutes, be warmed up to 110 DEG C, carry out three washings, the time is respectively 10
Minute, add hexane 60mL and wash twice, obtain solids 7.3g(solid constituent), containing Ti:3.2%, Mg:25.2%, Cl:
50.6%。
Embodiment 13
Identical with embodiment 12, simply with the compound 2 in embodiment, 4-dibenzoyl epoxide pentane is changed to 3,5-hexichol
Formyloxy pentane.
Embodiment 14
Identical with embodiment 12, simply with the compound 2 in embodiment, 4-dibenzoyl epoxide pentane is changed to 9,9-diformazan
Oxygen methyl fluorenes.
Embodiment 15
In the reactor being sufficiently displaced from through high pure nitrogen, add 400mLTiCl4, it is cooled to-20 DEG C, adds ethyoxyl
Magnesium 7.0g, when being warming up to 40 DEG C stage by stage under stirring, adds 2,4-dibenzoyl epoxide pentane (0.006 mole), maintains temperature 3
Hour, after filtration.Add TiCl4Compound 2-isopropyl-2-isopentyl-1 of 100mL and described structure, the double (triallyl of 3-
Siloxy) propane (0.006 mole), it is warmed up to 110 DEG C, carries out three times and process.Add hexane 60mL to wash three times.Consolidate
Body thing 6.7g(solid constituent), containing Ti:3.2%, Mg:23.6%, Cl:48.6%.
Embodiment 16
In the reactor being sufficiently displaced from through high pure nitrogen, add 400mLTiCl4, it is cooled to-20 DEG C, adds magnesium chloride
Alcohol adduct carrier 7.0g, when being warming up to 40 DEG C stage by stage under stirring, adds 2,4-dibenzoyl epoxide pentane (0.006 mole),
Maintain temperature 2 hours, after filtration.Add TiCl4Compound 2-isopropyl-2-isopentyl-1 of 100mL and described structure, 3-is double
(triallyl siloxy) propane (0.006 mole), stirs 1 hour, is warmed up to 110 DEG C, carries out three times and processes.Add hexane
60mL washs three times.Obtain solids 6.3g(solid constituent), 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 sufficiently displaced from, adds AlEt32.5mL, methylcyclohexyl
Dimethoxysilane (CHMMS) 5ml makes Al/Si(mol)=25, add above-described embodiment 6 preparation solid constituent 10mg and
1.8kg/cm2Hydrogen, is passed through liquid propene 2.5L, is warming up to 70 DEG C, maintains this temperature 1 hour, cooling, bleeds off pressure, and discharging obtains PP
Resin, activity 40600gPP/gCat., the isotacticity 97.6%(of resulting polymers see attached list 1).
Embodiment 18
With embodiment 17, simply by the solid group in solid constituent alternative embodiment 17 synthesized in above-described embodiment 7
Point.Concrete outcome sees attached list 1.
Embodiment 19
With embodiment 17, simply by the solid group in solid constituent alternative embodiment 17 synthesized in above-described embodiment 8
Point.Concrete outcome sees attached list 1.
Embodiment 20
With embodiment 17, simply by the solid group in solid constituent alternative embodiment 17 synthesized in above-described embodiment 9
Point.Concrete outcome sees attached list 1.
Embodiment 21
With embodiment 17, simply by the solid group in solid constituent alternative embodiment 17 synthesized in above-described embodiment 10
Point.Concrete outcome sees attached list 1.
Embodiment 22
With embodiment 17, simply by the solid group in solid constituent alternative embodiment 17 synthesized in above-described embodiment 11
Point.Concrete outcome sees attached list 1.
Embodiment 23
With embodiment 17, simply by the solid group in solid constituent alternative embodiment 17 synthesized in above-described embodiment 12
Point.Concrete outcome sees attached list 1.
Embodiment 24
With embodiment 17, simply by the solid group in solid constituent alternative embodiment 17 synthesized in above-described embodiment 13
Point.Concrete outcome sees attached list 1.
Embodiment 25
With embodiment 17, simply by the solid group in solid constituent alternative embodiment 17 synthesized in above-described embodiment 14
Point.Concrete outcome sees attached list 1.
Embodiment 26
With embodiment 17, simply by the solid group in solid constituent alternative embodiment 17 synthesized in above-described embodiment 15
Point.Concrete outcome sees attached list 1.
Embodiment 27
With embodiment 17, simply by the solid group in solid constituent alternative embodiment 17 synthesized in above-described embodiment 16
Point.Concrete outcome sees attached list 1.
Embodiment 28
With embodiment 17, simply polymerization reaction time in embodiment is extended for 2 hours.Concrete outcome sees attached list 1.
Embodiment 29
With embodiment 17, simply polymerization reaction time in embodiment is extended for 3 hours.Concrete outcome sees attached list 1.
Embodiment 30
With embodiment 23, simply polymerization reaction time in embodiment is extended for 2 hours.Concrete outcome sees attached list 1.
Embodiment 31
With embodiment 23, simply polymerization reaction time in embodiment is extended for 3 hours.Concrete outcome sees attached list 1.
Embodiment 32
With embodiment 24, simply polymerization reaction time in embodiment is extended for 2 hours.Concrete outcome sees attached list 1.
Embodiment 33
With embodiment 24, simply polymerization reaction time in embodiment is extended for 3 hours.Concrete outcome is shown in Table 1.
Table 1
Claims (23)
1., for a catalytic component for olefinic polymerization, it is with magnesium, titanium, halogen and internal electron donor as main component, described
Internal electron donor include the silane compound as shown in formula I:
R in formula1、R2、R3、R4Identical or different, for alkyl or the alkyl with vinyl of C2～C20 of C1～C20；R5、
R6Identical or different, for the alkyl of C1～C6 or the aralkyl of C6～C20 or the alkaryl of C6～C20；A is one or more taking
Generation or unsubstituted methylene, the cycloalkyl of C4～C20, the fragrant ring group of C5～C20 or polycyclic aromatic base；In n=0～6
Integer.
Catalytic component the most according to claim 1, it is characterised in that described silane compound is in following
One or more: 3-isopropyl-2,4-double (triallyl siloxy) pentane, 3-isopentyl-2, double (the triallyl silica of 4-
Base) pentane, 3-methyl-2,4-double (triallyl siloxy) pentane, 3-ethyl-2, double (triallyl siloxy) pentane of 4-,
3-butyl-2,4-double (triallyl siloxy) pentane, 3-benzyl-2, double (triallyl siloxy) pentane of 4-, 1,3-hexichol
Base-1, double (triallyl siloxy) propane of 3-, 1,3-diphenyl-2-ethyl-1, double (triallyl siloxy) propane of 3-, 1,
3-diphenyl-2-isopentyl-1, double (triallyl siloxy) propane of 3-, 1,3-diphenyl-2-butyl-1, double (three allyls of 3-
Base siloxy) propane, 1-methyl-2-butyl-3-phenyl-1, double (triallyl siloxy) propane of 3-, 1-methyl-3-phenyl-
1,3-double (triallyl siloxy) propane, 1,2-dimethyl-3-phenyl-1,3-double (triallyl siloxy) propane, 1-first
Base-2-isopropyl-3-phenyl-1,3-double (triallyl siloxy) propane, 1-methyl-3-phenyl-1, double (the triallyl silicon of 3-
Epoxide) propane, 1-methyl-2-ethyl-3-phenyl-1, double (triallyl siloxy) propane of 3-.
Catalytic component the most according to claim 1 and 2, it is characterised in that described internal electron donor also includes following
One or more in compound: diatomic alcohol acid ester compounds, diether compound, dibasic aliphatic carboxylic acid ester compound and
Aromatic polycarboxylic acid esters compound.
Catalytic component the most according to claim 3, it is characterised in that described diatomic alcohol acid ester compounds is selected from followingization
One or more in compound: 2,4-dibenzoyl epoxide pentanes, 3-methyl-2,4-dibenzoyl epoxide pentane, 3-ethyl-2,
4-dibenzoyl epoxide pentane, 3,5-dibenzoyl epoxide heptane, 4-ethyl-3,5-dibenzoyl epoxide heptane, 3-propyl group-1,
2-bis-(2-diisopropylbenzoyl peroxide epoxide) benzene, 3-methyl isophthalic acid, 2-bis-(2-diisopropylbenzoyl peroxide epoxide) benzene, 3-isopropyl-1,2-
Dibenzoyl epoxide benzene, 9,9-dibenzoyl oxygen methyl fluorenes, 2-isopropyl-2-isopentyl-1,3-dibenzoyl epoxide propane, 4-
Methyl-3,5-dibenzoyl epoxide heptane or 4-isopropyl-3,5-dibenzoyl epoxide heptane.
Catalytic component the most according to claim 3, it is characterised in that described diether compound is selected from following compound
In one or more: 2-isopropyl-2-isopentyl-1,3-dimethoxy propane, 2-isopropyl-2-isobutyl group-1,3-diformazan
Epoxide propane or 9,9-dimethoxy methyl fluorenes.
Catalytic component the most according to claim 3, it is characterised in that described dibasic aliphatic carboxylic acid ester compound selects
One or more in following compound: dibutyl succinate, 2-diethyl butylmalonate, ethyl glutarate or penta 2
Dibutyl phthalate.
Catalytic component the most according to claim 3, it is characterised in that described aromatic polycarboxylic acid esters compound selected from
One or more in lower compound: n-butyl phthalate, diethyl phthalate, phthalic acid two isobutyl
Ester, 3-methyl-dibutyl phthalate, amyl phthalate or dinoctyl phthalate.
8., according to a preparation method for the catalytic component according to any one of claim 1-7, comprise the following steps:
A) magnesium halide is dissolved in organic epoxy compound thing and organic phosphorus compound makes homogeneous solution, in dicyandiamide solution add or
It is added without inert diluent；Inert diluent is non-polar solven；
B) above-mentioned homogeneous solution is mixed with titanium tetrahalide or derivatives thereof, reaction system adds precipitation additive, solids
Separate out；
C) internal electron donor is attached on solids, then processes with titanium tetrahalide or inert diluent, then with shown in formula I
Silane compound process, obtain including the solid catalyst of titanium, magnesium, halogen and internal electron donor.
Preparation method the most according to claim 8, it is characterised in that described inert diluent is toluene.
Preparation method the most according to claim 8, it is characterised in that organic phosphorus compound described in step a) is phosphoric acid
Ester type compound, described phosphate compounds is tributyl phosphate, three iso-butyl ester of phosphoric acid, triethyl phosphate or TNPP tri n pentyl phosphate
In the mixture of one or more.
11. preparation methoies according to claim 8, it is characterised in that precipitation additive described in step b) is selected from followingization
One or more in compound: organic acid anhydride, organic acid, ether, ketone, diol-lipid；Wherein organic acid anhydride is acetic anhydride, adjacent benzene two
Formic anhydride, succinic anhydride, maleic anhydride or pyromellitic acid anhydride；Organic acid be acetic acid, propanoic acid, butanoic acid, acrylic acid or
Methacrylic acid；Ketone is acetone, butanone or benzophenone；Ether is that methyl ether, ether, propyl ether, butyl ether, amyl ether, 2-isopropyl-2-are different
Amyl group-1,3-dimethoxy propane or 9,9-dimethoxy methyl fluorenes；Diol-lipid is 2,4-dibenzoyl epoxide pentane or 3-second
Base-2,4-dibenzoyl epoxide pentane.
12. 1 kinds, according to the preparation method of the catalytic component according to any one of claim 1-7, comprise the following steps: will
Magnesium halide or organo-magnesium compound, alcohol compound and titanate ester or halogenated titanium compound are sufficiently mixed in atent solvent and stir
Mixing, after heating, cooling obtains ball-type carrier or addition atent solvent obtains uniform alcohol adduct solution；By above-mentioned carrier or uniform
Solution mixes with titanium tetrahalide or derivatives thereof, maintains a period of time post-heating to heat up, in adding at temperature is-80～0 DEG C
Electron donor, then process with titanium tetrahalide or inert diluent, then process by compounds of formula I, eventually pass filtration, wash
Wash, obtain after drying including the solid catalyst of the compositions such as titanium, magnesium, halogen, electron donor.
13. preparation methoies according to claim 12, it is characterised in that by above-mentioned carrier or homogeneous solution and titanium tetrahalide
Or derivatives thereof mix, temperature be-40～-10 DEG C at maintain a period of time post-heating heat up, addition internal electron donor.
14. preparation methoies according to claim 12, it is characterised in that described atent solvent is toluene.
15. preparation methoies described in any one in-14 according to Claim 8, it is characterised in that described ingredient of solid catalyst
In, based on every mole of magnesium compound, titanium compound is 0.3～100 mole；Internal electron donor compound≤15 mole.
16. preparation methoies according to claim 15, it is characterised in that described titanium compound is 5～20 moles.
17. preparation methoies according to claim 15, it is characterised in that described internal electron donor compound be 0.01～
0.5 mole.
18. 1 kinds of catalyst system and catalyzings containing the catalytic component according to any one of with good grounds claim 1-7, it is characterised in that
Described catalyst system and catalyzing comprises component i), component ii), wherein, component i) is ingredient of solid catalyst, component ii) it is organic calorize
Compound.
19. catalyst system and catalyzings according to claim 18, it is characterised in that described catalyst system and catalyzing is by component i), component ii) and
Component iii) composition, wherein, and component iii) it is organo-silicon compound.
20. according to the catalyst system and catalyzing described in claim 18 or 19, it is characterised in that the formula of described organo-aluminum compound is
AlRnX3-nAlkyl aluminum compound, in formula, R is hydrogen or carbon number is the alkyl of 1-20, and X is halogen, and n is the number of 1 < n≤3.
21. catalyst system and catalyzings according to claim 20, it is characterised in that described organo-aluminum compound is selected from following compound
In one or more: triethyl aluminum, three n-butylaluminum, triisobutyl aluminium, three n-heptyl aluminum, tri-propyl aluminum, tri-n-octylaluminium,
Aluminium diethyl monochloride, a hydrogen diisobutyl aluminum, a chlorine dibutyl aluminum, sesquialter ethylmercury chloride aluminum or ethyl aluminum dichloride.
22. catalyst system and catalyzings according to claim 21, it is characterised in that described organo-aluminum compound be triethyl aluminum and/
Or triisobutyl aluminium.
23. catalyst system and catalyzings according to claim 19, it is characterised in that described organo-silicon compound are in lower compound
One or more: Cyclohexylmethyldimethoxysilane, dimethoxydiphenylsilane, dicyclopentyl dimethoxyl silane
(DCPMMS), Dicyclohexyldimethoxysilane, cyclopentyl-trimethoxy-silane, tert-butyl trimethoxy silane, 2-ethyl piperazine
Piperidinyl trimethoxy silane, methyl-t-butyldimethoxysilane or 2-ethyl piperidine base t-butyldimethoxysilane.
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| CN111234069B (en) * | 2018-11-29 | 2022-10-21 | 中国石油化工股份有限公司 | Magnesium/titanium-containing solid catalyst component, preparation method thereof, olefin polymerization catalyst and application thereof |
| US11440980B2 (en) | 2020-07-22 | 2022-09-13 | Saudi Arabian Oil Company | Methods for forming ultra high molecular weight polyethylenes and methods for reducing contaminant content in such |
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