CN105622797A - Solid catalyst component used for olefin polymerization and catalyst used for olefin polymerization and application - Google Patents
Solid catalyst component used for olefin polymerization and catalyst used for olefin polymerization and application Download PDFInfo
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- CN105622797A CN105622797A CN201410610815.1A CN201410610815A CN105622797A CN 105622797 A CN105622797 A CN 105622797A CN 201410610815 A CN201410610815 A CN 201410610815A CN 105622797 A CN105622797 A CN 105622797A
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Abstract
The present invention relates to a solid catalyst component used for olefin polymerization and a catalyst used for the olefin polymerization and application. The solid catalyst component comprises titanium, magnesium and a compound shown as formula I; wherein R1 and R2 are each independently selected from hydrogen or C1-C4 alkyl group; and R3 is selected from C1-C4 alkyl group. The solid catalyst component for the olefin polymerization comprises reaction products of contact reaction of a titanium compound, a magnesium compound and a compound shown as the formula I. At the same time, the present invention also provides a catalyst for the olefin polymerization, the catalyst for the olefin polymerization comprises reaction products of a) the solid catalyst component and b) an alkyl aluminum compound shown as a general formula of AlRnX3-n, wherein R is hydrogen or C1-C20 hydrocarbyl, X is selected from c hlorine, bromine and iodine, and 1 <n<=3. The present invention also provides a pre-polymerization catalyst used for olefin polymerization and a method of olefin polymerization.
Description
Technical field
The present invention relates to catalyst technical field, particularly to the compound that a kind of fluorene group and carboxylate combine.
Background technology
It is known that using magnesium, titanium and electron donor as the solid titanium catalyst component of basis, can be used for CH2=CHR olefinic polyreaction, particularly can obtain higher yields and the polymer of higher stereospecificity in there is the alpha-olefine polymerizing of 3 carbon or more carbon atom, wherein electron donor compound is one of requisite composition in catalytic component, and is continuously updated the replacement along with the development of internal electron donor compound result in polyolefin catalyst. At present, disclose multiple electron donor compound in a large number, such as polybasic carboxylic acid, monocarboxylic esters or multi-carboxylate, anhydride, ketone, monoether or polyether, alcohol, amine etc. and derivant thereof, what wherein comparatively commonly use is the aromatic carboxylic acids esters of binary, for instance n-butyl phthalate or diisobutyl phthalate etc.
Chinese patent CN1306544A discloses a class dibasic aliphatic carboxylic acid ester compound-glutarate. Catalyst containing this kind of electron donor is used for alkene, particularly during propylene polymerization, it is possible to high yield obtains the polymer with high isotactic index. This kind of Donor compound can pass through the esterification of corresponding 1,3-propanedicarboxylic acid and obtain. But the synthesis of corresponding 1,3-propanedicarboxylic acid extremely difficult (J.Org.Chem.,58142, (1993) and ibid, 47,1445, (1982)), its process relates to multistep reaction, and yield is low, response time is long, severe reaction conditions, being difficult to control (as hydrolysis one step therein needs 24-48 hour, very easily generate a large amount of by-product diimine simultaneously), this just greatly limit the application of this compounds and catalyst. This kind of catalyst activity is still on the low side simultaneously, and the stereoregularity of resulting polymers remains to be further improved.
Summary of the invention
Therefore, the invention provides the catalyst of a kind of new ingredient of solid catalyst containing fluorene group and the electron donor compound of carboxylate combination and preparation thereof, its high comprehensive performance.
Ingredient of solid catalyst comprises titanium, magnesium and the electron donor compound such as formula I;
Wherein R1And R2It is each independently selected from the alkyl of hydrogen or C1��C4; R3Alkyl selected from C1��C4.
Owing to introducing fluorene group in the molecular structure of this kind of electron donor compound of the present invention, utilize the reactivity of fluorenes-9-position, simple organic chemical reactions can be passed easily through be synthetically derived, make catalyst preparing cost be substantially reduced, be conducive to industrialization promotion.
Described R in a specific embodiment, in the compound shown in formula I1And R2Select methyl or ethyl independently of one another.
Described R in a specific embodiment, in the compound shown in formula I3Selected from ethyl.
In a specific embodiment, the compound containing fluorene group and carboxylate combination shown in the formula I in above-mentioned ingredient of solid catalyst specifically includes: 2,2'-(9H-fluorenes-9,9-bis-base) oxalic acid dimethyl ester, 2,2'-(9H-fluorenes-9,9-two base) oxalic acid diethylester, 2,2'-(9H-fluorenes-9,9-two base) oxalic acid di-n-propyl ester, 2,2'-(9H-fluorenes-9,9-two base) oxalic acid diisopropyl ester, 2,2'-(9H-fluorenes-9,9-two base) oxalic acid di-n-butyl, 2,2'-(9H-fluorenes-9,9-two base) oxalic acid diisobutyl ester, 2,2'-(9H-fluorenes-9,9-two base) oxalic acid di tert butyl carbonate, 2,2'-(9H-fluorenes-9,9-two base) dipropionic acid dimethyl ester, 2,2'-(9H-fluorenes-9,9-two base) dipropionic acid diethylester, 2,2'-(9H-fluorenes-9,9-two base) dipropionic acid di-n-propyl ester, 2,2'-(9H-fluorenes-9,9-two base) dipropionic acid diisopropyl ester, 2,2'-(9H-fluorenes-9,9-two base) dipropionic acid di-n-butyl, 2,2'-(9H-fluorenes-9,9-two base) dipropionic acid diisobutyl ester, 2,2'-(9H-fluorenes-9,9-two base) dipropionic acid di tert butyl carbonate, 2,2'-(9H-fluorenes-9,9-two base) two butanoic acid dimethyl esters, 2,2'-(9H-fluorenes-9,9-two base) two butanoic acid diethylesters, 2,2'-(9H-fluorenes-9,9-two base) two butanoic acid di-n-propyl esters, 2,2'-(9H-fluorenes-9,9-two base) two butanoic acid diisopropyl esters, 2,2'-(9H-fluorenes-9,9-two base) two butanoic acid di-n-butyls, 2,2'-(9H-fluorenes-9,9-two base) two butanoic acid diisobutyl esters, 2,2'-(9H-fluorenes-9,9-two base) two butanoic acid di tert butyl carbonates, 2,2'-(9H-fluorenes-9,9-two base) diamyl dimethyl phthalate, 2,2'-(9H-fluorenes-9,9-two base) diamyl diethyl phthalate, 2,2'-(9H-fluorenes-9,9-two base) two valeric acid di-n-propyl esters, 2,2'-(9H-fluorenes-9,9-two base) two valeric acid diisopropyl esters, 2,2'-(9H-fluorenes-9,9-two base) two valeric acid di-n-butyls, 2,2'-(9H-fluorenes-9,9-two base) two valeric acid diisobutyl esters, 2,2'-(9H-fluorenes-9,9-two base) two valeric acid di tert butyl carbonates, 2,2'-(9H-fluorenes-9,9-two base) double, two (3 Methylbutanoic acid dimethyl esters), 2,2'-(9H-fluorenes-9,9-two base) double, two (3 Methylbutanoic acid diethylesters), 2,2'-(9H-fluorenes-9,9-two base) double, two (3 Methylbutanoic acid di-n-propyl esters), 2,2'-(9H-fluorenes-9,9-two base) double, two (3 Methylbutanoic acid diisopropyl esters), 2,2'-(9H-fluorenes-9,9-two base) double, two (3 Methylbutanoic acid di-n-butyls), 2,2'-(9H-fluorenes-9,9-two base) double, two (3 Methylbutanoic acid diisobutyl esters), 2,2'-(9H-fluorenes-9,9-two base) double, two (3 Methylbutanoic acid di tert butyl carbonates), 2,2'-(9H-fluorenes-9,9-two base) two caproic acid dimethyl esters, 2,2'-(9H-fluorenes-9,9-two base) two caproic acid diethylesters, 2,2'-(9H-fluorenes-9,9-two base) two caproic acid di-n-propyl esters, 2,2'-(9H-fluorenes-9,9-two base) two caproic acid diisopropyl esters, 2,2'-(9H-fluorenes-9,9-two base) two caproic acid di-n-butyls, 2,2'-(9H-fluorenes-9,9-two base) two caproic acid diisobutyl esters, 2,2'-(9H-fluorenes-9,9-two base) two caproic acid di tert butyl carbonates, 2,2'-(9H-fluorenes-9,9-two base) double, two (4-methylvaleric acid dimethyl ester), 2,2'-(9H-fluorenes-9,9-two base) double, two (4-methylvaleric acid diethylester), 2,2'-(9H-fluorenes-9,9-two base) double, two (4-methylvaleric acid di-n-propyl ester), 2,2'-(9H-fluorenes-9,9-two base) double, two (4-methylvaleric acid diisopropyl ester), 2,2'-(9H-fluorenes-9,9-two base) double, two (4-methylvaleric acid di-n-butyl), 2,2'-(9H-fluorenes-9,9-two base) double, two (4-methylvaleric acid diisobutyl ester), 2,2'-(9H-fluorenes-9,9-two base) double, two (4-methylvaleric acid di tert butyl carbonate), 2,2'-(9H-fluorenes-9,9-two base) double, two (3,3-dimethyl butyrate dimethyl phthalate), 2,2'-(9H-fluorenes-9,9-two base) double, two (3,3-dimethyl butyrate diethyl phthalate), 2,2'-(9H-fluorenes-9,9-two base) double, two (3,3-acid dimethyl di-n-propyl ester), 2,2'-(9H-fluorenes-9,9-two base) double, two (3,3-acid dimethyl diisopropyl ester), 2,2'-(9H-fluorenes-9,9-two base) double, two (3,3-acid dimethyl di-n-butyl), 2,2'-(9H-fluorenes-9,9-two base) double, two (3,3-acid dimethyl diisobutyl ester) and 2,2'-(9H-fluorenes-9,9-two base) double, two (3,3-acid dimethyl di tert butyl carbonates) etc.
In a specific embodiment, based on the gross weight of ingredient of solid catalyst, the content of the compound shown in described formula I is 3��25wt%, and the content of titanium is 1��8wt%, and the content of magnesium is 8��30wt%; The content of the compound shown in preferred described formula I is 5��25wt%, and the content of titanium is 1��6wt%, and the content of magnesium is 10��25wt%.
Present invention also offers the another kind of ingredient of solid catalyst for olefinic polymerization, it comprises titanium compound, magnesium compound and is selected from the compound shown in formula I by contacting the product obtained. Containing above-mentioned catalytic component in described product.
Magnesium compound therein selected from magnesium dihalide, the hydrate of alkoxyl magnesium alkyl magnesium magnesium dihalide, magnesium dihalide alcohol adduct, and in magnesium dihalide molecular formula one of them halogen atom by the replaced compound of oxyl or halo oxyl. It is preferably the alcohol adduct of magnesium dihalide or magnesium dihalide. Instantiation such as magnesium dichloride, dibrominated magnesium, magnesium diiodide and their alcohol adduct.
Titanium compound is formula is TiXm(OR1)4-mCompound, R in formula1For C1��C20Alkyl, X is selected from chlorine, bromine, iodine, 1��m��4, such as in 1,2,3 or 4 one of m. Formula is TiXm(OR1)4-mThe example of compound have titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium, it is preferable that titanium tetrachloride.
Ingredient of solid catalyst in the present invention, such as can prepare by the following method: first magnesium compound is dissolved in the dicyandiamide solution comprising organic epoxide, organic phosphorus compound and inert diluent composition, mix with titanium compound after forming homogeneous solution, under precipitation additive exists, precipitate out solids; This solids adopts the compound selected from formula I to process so that it is is attached on solids, if desired, then with titanium tetrahalide and inert diluent, solids is processed.
Compound shown in wherein said magnesium compound, titanium compound and formula I is as described in aforementioned. Described organic epoxy compound thing, organic phosphorus compound and precipitation additive etc. are disclosed in Chinese patent CN85100997, and its related content is incorporated herein by reference. As organic epoxide be selected from carbon number 2��8 aliphatic alkene, alkadienes or halogenated aliphatic alkene or the oxide of alkadienes, glycidyl ether and inner ether. Particular compound such as oxirane, expoxy propane, epoxy butane, butadiene oxide, butadiene double oxide, epoxychloropropane, methyl glycidyl ether, diglycidyl ether, oxolane. As organic phosphorus compound can include hydrocarbyl carbonate or the halohydrocarbyl ester of orthophosphoric acid or phosphorous acid, concrete such as orthophosphoric acid trimethyl, orthophosphoric acid triethyl, orthophosphoric acid tributyl, orthophosphoric acid triphenylmethyl methacrylate, NSC 6513, NSC 5284, tributyl phosphite, tricresyl phosphite benzene methyl. As described precipitation additive is selected from organic acid anhydride, organic acid, ether, ketone and ester. Specifically include as: acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic acid anhydride, acetic acid, propanoic acid, butanoic acid, acrylic acid, methacrylic acid, acetone, butanone, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether, succinate, malonate, glutarate, 2,4-pentadiol ester, 3,5-heptandiol ester. Described each component is in every mole of magnesium compound, the consumption of organic epoxy compound thing is 0.2��10 mole, the consumption of organic phosphorus compound is 0.1��3 mole, the consumption of precipitation additive is 0��1.0 mole, the consumption of titanium compound is 0.5��150 mole, and the consumption of the compound shown in described formula I is 0.01��1.0 mole.
Described ingredient of solid catalyst in the present invention is prepared also by additive method, the method that specifically can include being exemplified below:
Method one: as the method disclosed in patent CN1506384 prepares catalytic component. First, magnesium compound is mixed by 2��5 mol ratios and atent solvent with organic alcohol compound, be warming up to 120��150 DEG C, react 1��5 hour by magnesium/acid anhydride mol ratio 5��10. Then according to the alcohol adduct being cooled to room temperature is joined in the compound titanium solution being cooled to-15��-40 DEG C in advance by titanium/magnesium mol ratio 20��50, it is warming up to 90��110 DEG C, react 1��3 hour at 100��130 DEG C selected from the compound shown in formula I according to magnesium/internal electron donor mol ratio 2��10 addition is a kind of, filter to isolate solid particle. Joining in compound titanium solution according still further to titanium/magnesium mol ratio 20��50 by solid particle, stirring is also reacted 1.5��3 hours at 100��130 DEG C, filters to isolate solid particle. Finally wash solid particle with the atent solvent of 50��80 DEG C, obtain catalytic component after drying.
Method two: by titanium compound of the present invention is concrete such as TiCl4, it is MgCl with formula2The adduct of pROH reacts and prepares ingredient of solid catalyst. At MgCl2In pROH, p is the number of 0.1��6, it is preferable that 2��3.5, and R is the alkyl with 1��18 carbon atom. Adduct can be conveniently made spherical by the following method: under not miscible with adduct unreactive hydrocarbons exist, by alcohol (ROH) and MgCl2Mixing, makes the rapid chilling of this emulsion, so that adduct solidifies with the form of spheroidal particle. So obtained adduct can directly react with titanium compound, or it can first pass through the dealcoholization (80��130 DEG C) of thermal control with titanium compound in advance to obtain a kind of adduct before reacting, wherein the molal quantity of alcohol is generally below 3, it is preferable that between 0.1 and 2.7. Can pass through adduct (dealcoholysis or itself) is suspended in cold TiCl4In (general 0 DEG C), and by mixture temperature programming to 80��130 DEG C and keep at this temperature 0.1��2 hour, carry out the reaction with titanium compound. TiCl4Process can carry out once or repeatedly. With TiCl4Can adding above-mentioned compound of Formula I of the present invention during process to process, this process can also be repeated once or repeatedly.
Method three: the method disclosed in patent CN1091748 prepares catalytic component. Magnesium chloride alcohol adduct melt disperses through high-speed stirred in the dispersant system of white oil and silicone oil, forms emulsion, is discharged in coolant rapid cooling and shaping, formation magnesium chloride alcohol adduct microsphere. Coolant is the inert hydrocarbon solvent that boiling point is relatively low, such as petroleum ether, pentane, hexane, heptane etc. Gained magnesium chloride alcohol adduct microsphere is scrubbed, dry as ball type carrier, and the mol ratio of its alcohol and magnesium chloride is 2��3,2��2.5 as well. Diameter of carrier is 10��300 microns, best with 30��150 microns.
With excessive titanium tetrachloride at the above-mentioned ball type carrier of K cryogenic treatment, progressively heat up, processing procedure adds the electron donor shown in formula I of the present invention, repeatedly washs with atent solvent after process, obtain the spherical catalyst components of solid powdery after drying. The mol ratio of titanium tetrachloride and magnesium chloride is 20��200,30��60 as well; Initiated process temperature is-30��0 DEG C, is preferred with-25��-20 DEG C; Final treatment temperature is 80��136 DEG C, is preferred with 100��130 DEG C.
Method four: dialkoxy magnesium also can be used to add stirring in arene compound, form suspension; Suspension-20��100 DEG C of process with tetravalence titanium chloride, and 0��130 DEG C of reaction, in the process, adds formula I electron donors of the present invention at-20��130 DEG C and reacts, and the solid arene compound obtained washs; Then at 0��130 DEG C in aromatic hydrocarbon solvent, then process with tetravalence titanium chloride, finally wash with atent solvent, drain, obtain ingredient of solid catalyst. Wherein every mole of dialkyl magnesium tetravalence titanium chloride 0.5��100mol, electron donor is with 0.01��10mol.
Method five: use TiCl4Or two magnesium hydrocarbyloxy compound of such as dialkoxy magnesium or two aryloxy group magnesium etc are carried out halogenation by its arene solution at 80��130 DEG C, use TiCl4Or its arene solution carries out process and can be repeated once or repeatedly, and in the such process of one or many, add the compound of formula I of the present invention.
Method six: the method disclosed in patent US4540679 prepares catalytic component. First, magnesium alkoxide and carbon dioxide reaction prepare alkyl carbonic acid magnesium carrier. Then transistion metal compound (being preferably tetravalent titanium compound) and the electron donor of alkyl carbonic acid magnesium carrier and formula I of the present invention react in certain proportion in atent solvent, wherein transition metal is at least 0.5:1 with the mol ratio of magnesium elements, and the electron donor consumption of formula I of the present invention is up to 1.0 moles of every gram of titanium atoms. Atent solvent through purification, must easily make the material of catalyst poisoning sloughing water, oxygen, carbon dioxide etc. Reaction carries out at-10��170 DEG C, and the response time is a few minutes arrive several hours.
Preparing the method for ingredient of solid catalyst also just like by magnesium compound, electron donor etc. forms emulsion in diluent, adds titanium compound and makes its fixing spherical solid that obtains, and treated obtains ingredient of solid catalyst.
In any above-mentioned preparation method, namely required electron donor compound I can add with the form of compound; Can also adding in other manners, as passed through to adopt the electron donor compound I precursor original position being suitable for obtain, this front physical ability passes through the electron donor compound that example chemical reaction as is known such as esterification etc. becomes required.
According to another aspect of the present invention, providing again a kind of catalyst for olefinic polymerization, it comprises the product of following component:
A) above-mentioned ingredient of solid catalyst;
B) formula is AlRnX3-nAlkyl aluminum compound, wherein, in formula, R is hydrogen or C1��C20Alkyl, X one in chlorine, bromine, the iodine, 1 < n��3, for instance n is selected from 2 or 3.
In above-mentioned catalyst, the instantiation of described alkyl aluminum compound includes triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminum and ethyl aluminum dichloride, it is preferable that triethyl aluminum, triisobutyl aluminium.
When olefin polymer for needing stereoregularity significantly high is applied, for adding c) external electron donor in the component of the catalyst of olefinic polymerization, described external electron donor is R selected from formula2kSi(OR3)4-kCompound, wherein, R2And R3Can be identical or different, R3One in alkyl, cycloalkyl, aryl, haloalkyl, R2One in alkyl, cycloalkyl, aryl, haloalkyl, amino, substituted-amino, halogen and hydrogen atom, 0��k��3, as k is selected from 0,1,2,3. Halogen is selected from one or more in chlorine, bromine, iodine. Such as: trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, methyl-t-butyldimethoxysilane, it is preferable that Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane.
In above-mentioned catalyst, the mol ratio of component a) and component b) is with titanium: aluminum is calculated as 1:5��5000, it is preferable that 1:20��500. Component a) and c) mol ratio with titanium: silicon is calculated as 1:0��500, it is preferable that 1:3��100.
According to another aspect of the present invention, provide a kind of pre-polymerized catalyst for olefinic polymerization, described pre-polymerized catalyst comprises above-mentioned catalyst and alkene and carries out the prepolymer of prepolymerization gained, and pre-polymerization multiple is 0.1��1000g olefin polymer/g ingredient of solid catalyst.
In the present invention, " pre-polymerized catalyst " refers to the relatively low transforming degree catalyst through polymerization procedure. According to the present invention it is possible to adopt the alpha-olefin identical with polymerization alkene used to carry out prepolymerization, wherein carry out prepolymerized alkene and be preferably ethylene or propylene. Specifically, it is therefore particularly preferred that adopt ethylene or its carry out prepolymerization with measuring the mixture of one or more alpha-olefins being up to 20mol%. Preferably, the transforming degree of pre-polymerized catalyst components is about 0.2��500 gram of polymer/gram ingredient of solid catalyst.
Prepolymerization operation can at-20 to 80 DEG C, it is preferable that at the temperature of 0��50 DEG C, in a liquid or carry out in gas phase. Prepolymerization step can carry out online as the part in continuous polymerization technique, or carries out independently in intermittently operated. For the polymer that preparation amount is 0.5��20g/g catalytic component, it is particularly preferred to the batch pre-polymerization of catalyst of the present invention and ethylene. Polymerization pressure is 0.01��10MPa.
According to a further aspect in the invention, it is provided that a kind of olefine polymerizing process, wherein said alkene is polymerized under the effect of above-mentioned catalyst or pre-polymerized catalyst.
The catalyst of the present invention can be directly added in reactor in polymerization process, or catalyst and alkene pre-polymerization obtain pre-polymerized catalyst after add in reactor.
The olefinic polyreaction of the present invention carries out according to known polymerization, it is possible to carry out in liquid phase or gas phase, or can also carry out under the operation of liquid and gas polymerization stage combination. Adopt conventional technology such as slurry process, gas-phase fluidized-bed etc. It it is adopt following reaction condition preferably: polymerization temperature 0��150 DEG C, it is preferable that 60��90 DEG C. In a specific embodiment, described in be polymerized to liquid phase polymerization.
In the present invention, the formula of alkene is CH2=CHR, wherein R is hydrogen or C1��C12Alkyl or aryl. Alkene is as selected from ethylene, propylene, 1-butylene, 4-methyl-1-pentene and 1-hexene; It preferably is selected from ethylene or propylene. As propylene all polymerizations with or the combined polymerization of other alkene of propylene. The inventive method is also applied for the homopolymerization such as ethylene and ethylene and alpha-olefin, as propylene, butylene, amylene, hexene, octene, 4-methyl-1-pentene copolymerization.
The compound that fluorene group in catalyst provided by the invention and carboxylate combine, its simple in construction, after hydrogenation reaction, dialkyl can be carried out with corresponding alpha-halogenated carboxylic acids ester by the raw material 9H-fluorenes being easy to get and obtain. Its preparation process mild condition, simple to operate and yield is high, the process of the compound in the preparation present invention provides cost savings simultaneously, and then, use described compound to also reduce catalyst preparing cost for field of olefin polymerisation.
The highly crystallized owing to propylene polymer structures is regular, thus, heat-resisting, corrosion-resistant, the sterilization of goods used vapour is its outstanding advantages. Polyacrylic isotactic index prepared by the compound in comparative example 1 is 95.08%, and polyacrylic isotactic index 96.12% prepared by the compound in the present invention, it has exceeded about one percentage point than the isotactic index in comparative example. It is to say, comprise the compound of the present invention for olefinic polymerization, especially during propylene polymerization, having higher activity, the stereoregularity of resulting polymers is good, thus the compound of the present invention is for the high comprehensive performance of olefinic polymerization. Those skilled in the art is readily understood by, the raising of isotactic index of the prior art is in bottleneck, say, that if increased by isotactic index on the basis of existing technology again, even raising one percentage point, its difficulty is also very big. And the application is found that the compound that a class is new, it can improve the isotactic index of polymer, thus improve the quality of polymer, thus its beneficial effect is also very big, and it has good application prospect.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described below.
One, the synthesis of compound
Compound (1)
The compound (1) that the fluorene group of synthesis and carboxylate combine has a structure that
Under nitrogen protection, 250ml there-necked flask adds 5mmol9H-fluorenes, 35mlDMF, stirring and dissolving. Add 30mmol Sodium ethylate, stirring reaction 2 hours. Instill 30mmol bromoacetate under room temperature, react 4 hours. Reactant liquor is poured in frozen water. Use CH2Cl2Extracting, extracting solution is through washing, anhydrous MgSO4Dry. Concentrating under reduced pressure removes solvent, obtains orange/red oil crude material. Doing eluant with ethyl acetate-light petrol, through flash column chromatography, obtain pure target compound, 2,2'-(9H-fluorenes-9,9-bis-base) oxalic acid diethylester, yield is 98.6%.
Compound (2)��(4)
According to the synthetic method similar to above-claimed cpd (1), alpha-brominated carboxylate and the 9H-fluorenes of selecting the replacement of different structural formula A are raw material, are synthetically derived a series of fluorene group with formula I and compound (2)��(4) of carboxylate combination. Wherein, 2,2'-(9H-fluorenes-9,9-bis-base) yield of oxalic acid di-n-propyl ester is 99.1%, 2,2'-(9H-fluorenes-9,9-bis-base) yield of oxalic acid diisopropyl ester is 97.9%, the yield of 2,2'-(9H-fluorenes-9,9-bis-base) dipropionic acid di-n-butyl is 98.3%. And use1HNMR confirms the structure of synthesized compound. R in the alpha-brominated carboxylate A replaced and product structure Formulas I1��R2And R3In Table 1.
Two, method of testing
The mensuration of nuclear magnetic resonance, NMR: use BrukerAVANCE300 nuclear magnetic resonance analyser Instrument measuring1H-NMR (300MHz, solvent C DCl3, TMS is interior mark, measures temperature 300K), result is in Table 1.
The compound that table 1 fluorene group and carboxylate combine
Embodiment 1
In the reactor being sufficiently displaced from through high pure nitrogen, it is sequentially added into magnesium chloride 4.8g, toluene 95mL, epoxychloropropane 4mL, tributyl phosphate 12.5mL, is warming up to 50 DEG C, and maintains 2.5h under stirring, solid is completely dissolved, and adds phthalic anhydride 1.4g, continues to 1h. Solution is cooled to less than-25 DEG C, dropping TiCl in 1h456mL, it is to slowly warm up to 80 DEG C, temperature-rise period precipitates out solids gradually, adding the compound (1) 2 of the above-mentioned preparation of 6mmol, 2'-(9H-fluorenes-9,9-bis-base) oxalic acid diethylester is as internal electron donor, maintain temperature 1h, after filtration, wash twice with toluene 70mL respectively, obtain solid sediment. It is subsequently adding toluene 60mL, TiCl440mL, is warmed up to 110 DEG C, maintains 2h, and after venting filtrate, same operation is repeated once, and again with toluene 70mL washs three times at 110 DEG C, and the time is respectively 10min, adds hexane 60mL, washes twice. Obtain ingredient of solid catalyst.
Polyreaction carries out in 5L rustless steel autoclave. First by polymeric kettle pressure-emptying close to after gauge pressure 0, now catalyst addition hopper nitrogen protection, and polymeric kettle tail gas bottle is protected. It is sequentially added into triethyl aluminum 2.5mmol at the low rotational speed, external electron donor Cyclohexylmethyldimethoxysilane 0.1mmol, catalyst (solid constituent is about 8-10mg), after of short duration pre-complexation, add reactor, add a certain amount of hydrogen and 2.3L liquid propylene afterwards, start to warm up, speed of agitator is increased to 350 revs/min, rise to 70 degree and maintain one hour, stirring is stopped when reaction terminates, cooling, pressure release, discharging obtains solid acrylic polymers. Without special instruction, n (Al): n (Si)=25, hydrogen usage P (H2)=0.2MPa (580mlH2Tank).
Polymer isotactic index measures: adopt heptane extraction process to measure (heptane boiling extracting 6 hours): polymer samples 2 grams dry, it is placed in extractor with, after boiling heptane extracting 6 hours, residue being dried to the polymer weight (g) of constant weight gained and is isotactic index with the ratio of 2. Test data is in Table 2.
Embodiment 2
With embodiment 1, it is different in that added internal electron donor is compound (2): 2,2'-(9H-fluorenes-9,9-bis-base) oxalic acid di-n-propyl ester. Data are in Table 2.
Embodiment 3
With embodiment 1, it is different in that added internal electron donor is compound (3): 2,2'-(9H-fluorenes-9,9-bis-base) oxalic acid diisopropyl ester. Data are in Table 2.
Embodiment 4
With embodiment 1, it is different in that added internal electron donor is compound (4): 2,2'-(9H-fluorenes-9,9-bis-base) dipropionic acid di-n-butyl. Data are in Table 2.
Comparative example 1
With embodiment 1, it is different in that added internal electron donor is glutarate compound: 3,3-diisobutyl ethyl glutarates. Data are in Table 2.
Table 2 catalyst propylene polymerization result
As can be seen from Table 2, adopt the compound combined containing fluorene group and carboxylate provided by the invention as electron donor, the ingredient of solid catalyst of preparation and catalyst are for olefinic polymerization, there is isotacticity active and higher preferably, such as embodiment 1, the activity of catalyst and polymer isotacticity are above comparative example 1, and the isotactic index of embodiment 2 has exceeded 2.45 percentage points than comparative example 1.
It should be noted that, embodiment described above is only used for explaining the present invention, it is not intended that any limitation of the invention. By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive and explanatory vocabulary, rather than limited vocabulary. Within the scope of the claims the present invention can be modified by regulation, and in without departing substantially from scope and spirit of the present invention, the present invention be revised. Although the present invention described in it relates to specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, the present invention can be extended to other all methods and applications with identical function.
Claims (12)
1., for an ingredient of solid catalyst for olefinic polymerization, it comprises titanium, magnesium and the compound such as formula I;
Wherein R1And R2It is each independently selected from the alkyl of hydrogen or C1��C4; R3Alkyl selected from C1��C4.
2. catalytic component according to claim 1, it is characterised in that described R1And R2It is each independently selected from methyl or ethyl; And/or described R3Selected from ethyl.
3. catalytic component according to claim 1 and 2, it is characterised in that based on the gross weight of ingredient of solid catalyst, the content of the compound shown in described formula I is 3��25wt%, and the content of titanium is 1��8wt%, and the content of magnesium is 8��30wt%; The content of the compound shown in preferred described formula I is 5��25wt%, and the content of titanium is 1��6wt%, and the content of magnesium is 10��25wt%.
4., for an ingredient of solid catalyst for olefinic polymerization, it comprises titanium compound, magnesium compound and is selected from the compound shown in formula I by contacting the product obtained;
Wherein said magnesium compound selected from magnesium dihalide, the hydrate of alkoxyl magnesium alkyl magnesium magnesium dihalide, magnesium dihalide alcohol adduct, and one of them halogen atom in magnesium dihalide molecular formula is by the replaced compound of oxyl or halo oxyl;
Described titanium compound is formula is TiXm(OR1)4-mCompound, R in formula1For C1��C20Alkyl, X be selected from chlorine, bromine, iodine, 1��m��4.
5., for a catalyst for olefinic polymerization, it comprises the product of following component:
A) ingredient of solid catalyst described in any one in claim 1-4;
B) formula is AlRnX3-nAlkyl aluminum compound, wherein, in formula, R is hydrogen or C1��C20Alkyl, X one in chlorine, bromine, the iodine, 1 < n��3.
6. catalyst according to claim 5, it is characterised in that described component also includes c) external electron donor, described external electron donor is R selected from formula2kSi(OR3)4-kCompound, wherein, R3One in alkyl, cycloalkyl, aryl, haloalkyl, R2One in alkyl, cycloalkyl, aryl, haloalkyl, amino, substituted-amino, halogen and hydrogen atom, 0��k��3.
7. the catalyst according to claim 5 or 6, it is characterised in that described component a) and b) mol ratio with titanium: aluminum is calculated as 1:5��5000, it is preferable that 1:20��500.
8. catalyst according to claim 6, it is characterised in that described component a) and c) mol ratio with titanium: silicon is calculated as 1:0��500, it is preferable that 1:3��100.
9. the pre-polymerized catalyst for olefinic polymerization, described pre-polymerized catalyst comprises catalyst according to any one in claim 5-8 and alkene and carries out the prepolymer of prepolymerization gained, and pre-polymerization multiple is 0.1��1000g olefin polymer/g ingredient of solid catalyst.
10. pre-polymerized catalyst according to claim 9, it is characterised in that alkene used by prepolymerization is ethylene or propylene.
11. a method for olefinic polymerization, described alkene is wherein made to be polymerized under the effect of the catalyst described in any one or the pre-polymerized catalyst described in claim 9 or 10 in claim 5-8.
12. method according to claim 11, it is characterised in that the formula of described alkene is CH2=CHR, wherein R is hydrogen or C1��C12Alkyl or aryl, described alkene preferably is selected from ethylene or propylene.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298887A (en) * | 1999-12-06 | 2001-06-13 | 中国石油化工集团公司 | Catalyst system for polymerization or copolymerization of olefine |
| WO2014050738A1 (en) * | 2012-09-28 | 2014-04-03 | ダイトーケミックス株式会社 | Fluorene-type compound, photopolymerization initiator comprising said fluorene-type compound, and photosensitive composition containing said photopolymerization initiator |
| CN104058967A (en) * | 2014-06-13 | 2014-09-24 | 北京利和知信科技有限公司 | Unsaturated cyclosubstituted diacid ester compound suitable for preparing olefin polymerization catalyst |
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2014
- 2014-11-03 CN CN201410610815.1A patent/CN105622797A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298887A (en) * | 1999-12-06 | 2001-06-13 | 中国石油化工集团公司 | Catalyst system for polymerization or copolymerization of olefine |
| WO2014050738A1 (en) * | 2012-09-28 | 2014-04-03 | ダイトーケミックス株式会社 | Fluorene-type compound, photopolymerization initiator comprising said fluorene-type compound, and photosensitive composition containing said photopolymerization initiator |
| CN104058967A (en) * | 2014-06-13 | 2014-09-24 | 北京利和知信科技有限公司 | Unsaturated cyclosubstituted diacid ester compound suitable for preparing olefin polymerization catalyst |
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| Title |
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| 许招会等: "聚丙烯催化剂内给电子体9,9-双(乙酸甲酯基)芴的合成与表征", 《石油炼制与化工》 * |
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