CN102040684A - Catalyst component for olefin polymerization reaction and catalyst thereof - Google Patents
Catalyst component for olefin polymerization reaction and catalyst thereof Download PDFInfo
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- CN102040684A CN102040684A CN 200910236267 CN200910236267A CN102040684A CN 102040684 A CN102040684 A CN 102040684A CN 200910236267 CN200910236267 CN 200910236267 CN 200910236267 A CN200910236267 A CN 200910236267A CN 102040684 A CN102040684 A CN 102040684A
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Abstract
The invention provides a catalyst component for an olefin polymerization reaction and a catalyst thereof. The catalyst component comprises magnesium, titanium, halogen and an electron donor, wherein the electron donor is at least one type of diethers compounds shown in the following general formula (I) in the specification, and the in the formula: R is a C1-C10 alkyl; R1 is a linear-chain or branched-chain primary alkyl of C1-C7, and H is optionally substituted by a heteroatom which is selected from F, C1, Br and I; R2 is a C6-C10 aryl, aralkyl or alkaryl, or a (R3R4)-CH-CH2-group, wherein the R3 and R4 group, which is same or different, is C1-C10 linear-chain alkyl or cycloalkyl formed by connecting the R3 and R4 to one another, and is CH3 when the R3 and the R4 are different. When the catalyst is used for polymerizing propylene, a satisfactory polymerization yield can be obtained and the molecular weight distribution of the polymer is wider.
Description
Technical field
The present invention relates to a kind of ingredient of solid catalyst that contains the diether compound of special construction, contain the catalyzer of this ingredient of solid catalyst and this catalyzer at CH
2Application in the=CHR olefinic polyreaction, wherein R is hydrogen or C
1～C
6Alkyl or aryl, special application in propylene polymerization can obtain that yield is higher, isotactic is higher and the polymkeric substance of molecular weight distribution broad.
Technical background
As everyone knows, with magnesium, titanium, halogen and electron donor solid titanium catalyst component, can be used for CH as basal component
2=CHR olefinic polyreaction, particularly in alpha-olefine polymerizing, can obtain the polymkeric substance of higher yields and higher tacticity with 3 carbon or more carbon atoms, wherein the electron donor compound is one of requisite composition in the catalyst component, and along with the development of internal electron donor compound has caused polyolefin catalyst constantly to update.At present, multiple electron donor compound is disclosed in a large number, for example polycarboxylic acid, monocarboxylic ester or multi-carboxylate, acid anhydrides, ketone, monoether or polyether, alcohol, amine etc. and derivative thereof, wherein comparatively commonly used is aromatic carboxylates's class of binary, for example n-butyl phthalate or diisobutyl phthalate etc. can be referring to Chinese patent CN85100997A.
In recent years, people attempt to adopt other compound to use as the electron donor in the olefin polymerization catalyst components again, for example at Chinese patent CN96107325.X and the disclosed catalyst component that is used for olefinic polyreaction of CN89107675.1, adopted and contained 1 of two ether groups, the 3-diether compound is as electron donor, 2-sec.-propyl-2-isopentyl-1 for example, 3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal and 9,9-two (methoxymethyl) fluorenes etc.Yet above-mentioned disclosed catalyzer also exists some and makes us not too satisfied defective in the practical application of olefinic polymerization, especially contains the catalyzer of two ethers internal electron donors, the defective of ubiquity narrow molecular weight distribution.The inventor unexpectedly finds, in olefin polymerization catalysis by using a kind of new diether compound that contains special construction as electron donor, can obtain the catalyzer of high comprehensive performance, when being used for propylene polymerization, can obtain gratifying polymerization yield rate, kept and contained originally outside the hydrogen response of diether catalyst, can also make the molecular weight distribution broad of resulting polymers, very favourable to the exploitation of different trade mark resins.
Summary of the invention
One of purpose of the present invention is to provide a kind of CH of being used for
2The catalyst component of=CHR olefinic polyreaction, wherein R is hydrogen or C
1～C
6Alkyl or aryl, this catalyst component comprises magnesium, titanium, halogen and electron donor, this electron donor is selected from least a diether compound in the following general formula (I):
In the formula: R is C
1～C
10Alkyl;
R
1Be a kind of C
1～C
7The primary alkyl of straight or branched, H are wherein randomly replaced by a heteroatoms, and described heteroatoms is selected from F, Cl, Br, I;
R
2Be C
6～C
10Aryl, aralkyl or alkaryl or (R
3R
4)-CH-CH
2-group, wherein R
3, R
4Group, identical or different, be C
1-C
10Straight chained alkyl, H are wherein randomly replaced by a heteroatoms, and described heteroatoms is selected from F, Cl, Br, I, or R
3With R
4Formation cycloalkyl and R are connected with each other
3With R
4Not CH simultaneously
3
Preferably, R in the general formula (I)
1Be C
1～C
7The alkyl of straight or branched or contain the alkyl of a heteroatomic straight or branched.Particularly, R
1Be selected from methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or amyl group, isopentyl, allyl group, butenyl and their halides.
Preferably, preferably methyl, ethyl of R in the general formula (I).
Preferably, R in the general formula (I)
2Preferably from phenyl, benzyl, 2-ethyl-butyl, 2-methyl butyl, 2-ethylhexyl, cyclopropyl methyl or cyclobutylmethyl.
The specific examples of diether compound of the present invention comprises:
2-methyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-ethyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-phenyl-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-methyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-ethyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-benzyl-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-methyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-ethyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-methyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-ethyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-methyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-ethyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-methyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-ethyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-propyl group-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-isobutyl--2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-isopentyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-methyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-ethyl-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal.
Of the present invention 1, the 3-diether compound can be with reference to disclosed preparation method's preparation among the european patent application No0361493.
The ingredient of solid catalyst that is used for olefinic polymerization of the present invention preferably comprises titanium compound, magnesium compound and is selected from the reaction product of the diether compound with above-mentioned general formula (I).
Wherein used magnesium compound is selected from a kind of by in-oxyl or the halo-oxyl institute metathetical derivative of one of them halogen atom in the hydrate of magnesium dihalide, magnesium dihalide or alcohol adduct and the magnesium dihalide molecular formula, or their mixture.The alcohol adduct of preferred magnesium dihalide or magnesium dihalide, for example magnesium dichloride, dibrominated magnesium, two magnesium iodides and their alcohol adduct.
It is TiX that wherein used titanium compound can be selected general formula for use
n(OR)
4-nCompound, R is that carbonatoms is 1～20 alkyl in the formula, X is a halogen, n=1～4.For example: titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, preferred titanium tetrachloride.
What particularly point out is magnesium compound, preferably is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds.Wherein organic epoxy compounds comprises at least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halo fat group alkene or diolefine of carbonatoms.Particular compound is as oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF).
Wherein organo phosphorous compounds comprises the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid, concrete as: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, tricresyl phosphite benzene methyl.
Can select to press the method for stating and prepare ingredient of solid catalyst of the present invention.
At first, magnesium compound is dissolved in the solvent system of being made up of organic epoxy compounds, organo phosphorous compounds and inert diluent, mixes with titanium compound behind the formation homogeneous solution, in the presence of precipitation additive, separate out solids; This solids by using is selected from the diether compound of general formula (I) and handles, it is attached on the solids, in case of necessity, with titanium tetrahalide and inert diluent solids is handled again, wherein precipitation additive can be selected a kind of in organic acid anhydride, organic acid, ether, the ketone or their mixture for use.Concrete as: diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, acetone, methylethylketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether.
Above-mentioned organic epoxy compounds, organo phosphorous compounds and precipitation additive etc. are disclosed among the Chinese patent CN85100997, and its associated viscera is incorporated herein by reference.
Described each component is in every mole of magnesium halide, organic epoxy compounds is 0.2～10 mole, and organo phosphorous compounds is 0.1～3 mole, and precipitation additive is 0～1.0 mole, titanium compound is 0.5～150 mole, and the diether compound of general formula (I) is 0.02～0.4 mole.
According to another kind of method, be to be TiX with general formula
n(OR)
4-nTitanium compound, R is that carbonatoms is 1～20 alkyl in the formula, X is a halogen, n=1～4, preferred TiCl
4, with general formula be MgCl
2The adducts of pROH reacts and the preparation ingredient of solid catalyst.At MgCl
2Among the pROH, p is 0.1～6 number, and is preferred 2～3.5, and R is the alkyl with 1～18 carbon atom.Adducts can be made spherical by the following method aptly: not with the miscible unreactive hydrocarbons of adducts in the presence of, pure and mild magnesium halide is mixed, make the rapid chilling of this emulsion, thereby adducts solidified with the form of spheroidal particle.The adducts that so obtains can be directly and the titanium compound reaction, perhaps it can pass through the dealcoholization (80～130 ℃) of thermal control to obtain a kind of adducts in advance before reacting with titanium compound, wherein Chun mole number generally is lower than 3, preferably between 0.1～2.7.Can be by adducts (dealcoholysis or itself) be suspended in cold TiCl
4In (general 0 ℃), and with mixture temperature programming to 80～130 ℃ and under this temperature, keep carrying out in 0.1～2 hour reaction with titanium compound.TiCl
4Processing can be carried out once or repeatedly.Using TiCl
4Can add above-mentioned general formula diether compound of the present invention during the processing and handle, this processing also can repeat once or repeatedly.
Another object of the present invention is to provide a kind of CH of being used for
2The catalyzer of=CHR olefinic polyreaction, wherein R is hydrogen or C
1～C
6Alkyl or aryl, comprise the reaction product of following component:
(1) a kind of above-mentioned containing magnesium, titanium, halogen and be selected from 1 of general formula (I), the ingredient of solid catalyst of 3-diether compounds;
(2) alkylaluminium cpd;
(3) randomly, external electron donor component.
Wherein alkylaluminium cpd is that general formula is AlR
nX
3-nCompound, R is a hydrogen in the formula, carbonatoms is 1～20 alkyl, X is a halogen, n is the number of 1＜n＜3; Specifically can be selected from 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 ethyl aluminum chloride, ethyl aluminum dichloride, preferred triethyl aluminum, triisobutyl aluminium.
When needing the very high olefin polymer of taxis to use, need to add (3) external electron donor compound, for example general formula is R
nSi (OR`)
4-nSilicoorganic compound, 0≤n in the formula≤3, R is of the same race or different alkyl, cycloalkyl, aryl, haloalkyls with R, R also can be halogen or hydrogen atom.For example: trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane, cyclohexyl methyl dimethoxy silane, methyl-t-butyldimethoxysilane, preferred cyclohexyl methyl dimethoxy silane, dimethoxydiphenylsilane.
The ratio between component (1), component (2) and the component (3) wherein, with titanium: aluminium: the molar ratio computing between the silicon is 1: (5～1000): (0～500); Be preferably 1: (25～100): (25～100).
Above-mentioned external electron donor component also can be selected from monobasic or polybasic organic acid ester, for example monobasic or polybasic benzoates.Preferred monobasic benzoates.
1 of the also optional self-drifting of above-mentioned external electron donor component (IV), 3-two ethers:
R wherein
I, R
II, R
III, R
IV, R
VAnd R
VIIdentical or different, for hydrogen or have the hydrocarbyl group of 1 to 18 carbon atom, and R
VIIAnd R
VIIICan be identical or different, for having the hydrocarbyl group of 1～18 carbon atom; R
I-R
VIIIGroup in one or morely can link up into ring.Preferably, R
VIIAnd R
VIIIBe selected from C
1-C
4Alkyl group, R
IIIAnd R
IVForm undersaturated condensed ring, and R
I, R
II, R
V, and R
VIBe hydrogen.For example: 9,9-bi-methoxy methyl fluorenes.
Olefinic polyreaction of the present invention carries out according to known polymerization process, can carry out in liquid phase or gas phase, perhaps also can carry out under the operation of liquid and gas polymerization stage combination.Adopt conventional technology such as slurry process, gas-phase fluidized-bed etc., wherein alkene is selected from ethene, propylene, 1-butylene, 4-methyl-1-pentene and 1-hexene, the equal polymerization of special propylene with or the copolymerization of other alkene of propylene.Be to adopt following reaction conditions preferably.
Polymerization temperature: 0～150 ℃, preferred 60～90 ℃.
Catalyzer of the present invention can directly add and be used for polymerization process in the reactor, and perhaps catalyzer can carry out prepolymerization before adding first polymerization reactor.In the present invention, term " pre-polymerized catalyst " means with the catalyzer of low transforming degree through polymerization procedure.According to the present invention, described pre-polymerized catalyst comprises the prepolymer that above-mentioned ingredient of solid catalyst and alkene carry out the prepolymerization gained, and the pre-polymerization multiple is 0.1～1000g olefin polymer/g ingredient of solid catalyst.
Can adopt the alpha-olefin identical to carry out prepolymerization, wherein carry out prepolymerized alkene and be preferably ethene or propylene with aforementioned alkene.Specifically, particularly preferably be, the mixture that adopts ethene or itself and amount to be up to one or more alpha-olefins of 20mol% carries out prepolymerization.Preferably, the transforming degree of pre-polymerized catalyst components is that about 0.2 gram is to about 500 gram polymkeric substance/gram ingredients of solid catalyst.
The prepolymerization operation can under preferred 0～50 ℃ temperature, be carried out in liquid or in the gas phase at-20 to 80 ℃.Prepolymerization step can be used as online the carrying out of a part in the continuous polymerization technique, or carries out independently in periodical operation.For preparation amount is the polymkeric substance of 0.5～20g/g catalyst component, the batch pre-polymerization of preferred especially catalyzer of the present invention and ethene.Polymerization pressure is 0.01～10MPa.
Catalyzer of the present invention also is applicable to produces polyethylene and ethene and alpha-olefin, as the multipolymer of propylene, butylene, amylene, hexene, octene, 4-methyl-1-pentene.
It is worthy of note that the present invention is by adopting novel internal electron donor diether compound, can obtain the catalyzer of high comprehensive performance, when being used for propylene polymerization, except can obtaining gratifying polymerization yield rate, the molecular weight distribution broad of its gained helps the post-production of polymkeric substance and develops new product grade.
Embodiment
Embodiment given below is for the present invention is described, rather than limits the invention.Testing method:
1, the mensuration of nucleus magnetic resonance: use Bruke dmx300 nuclear magnetic resonance analyser Instrument measuring
1H-NMR (300MHz, solvent C DCl
3, TMS is interior mark, measures temperature 300K).
2, the polymkeric substance degree of isotacticity adopts the heptane extraction process to measure (heptane boiling extracting 6 hours): 2 gram exsiccant polymer samples, be placed in the extractor with the extracting of boiling heptane after 6 hours, the polymer weight (g) that residuum is dried to the constant weight gained is degree of isotacticity with 2 ratio.
3, molecular weight distribution: use PL-GPC 220 to measure.
One, compound is synthetic:
Embodiment 12-n-pentyl-2-(2-ethylhexyl)-1, the preparation of 3-Propanal dimethyl acetal
A) preparation of 2-n-pentyl-2-(2-ethylhexyl) diethyl malonate
Under nitrogen gas stream, 60 milliliters of dehydrated alcohols and 3 gram (0.13 mole) sodium are joined agitator is housed, condenser, in 250 milliliters the flask of thermometer and airway, after sodium dissolves fully, input 16 gram (0.1 mole) diethyl malonates, at room temperature stir several minutes, add 16 milliliters of 1-bromo pentane silanes (0.12 mole) then, mixture under agitation refluxed 6 hours, thereafter, add 7.5 gram dehydrated alcohol sodium and 24 milliliters of (0.12 mole) 1-bromo-2-ethyl hexanes, continuing stirring heating refluxed 8 hours, underpressure distillation goes out most of solvent then, residue is with 200 milliliters of ether extraction, remove ether solvent after underpressure distillation get 17 gram 2-n-pentyl-2-(2-ethylhexyl) diethyl malonates.
B) 2-n-pentyl-2-(2-ethylhexyl)-1, the preparation of ammediol
Under nitrogen protection; in 250 milliliters the flask that agitator, condenser, thermometer and airway are housed, add 100 milliliters of anhydrous diethyl ethers and 3 gram lithium aluminum hydrides; under vigorous stirring; dropwise add 17 gram 2-n-pentyl-2-(2-ethylhexyl) diethyl malonates of above-mentioned preparation, reflux is 3 hours then, thereafter; the reaction mixture correct copy is contained in the useful dilute hydrochloric acid acidifying 100 gram mixture of ice and water; with ether extraction three times, evaporate ether, make 10 gram products.
C) 2-n-pentyl-2-(2-ethylhexyl)-1, the preparation of 3-Propanal dimethyl acetal
Under condition of nitrogen gas, 10 gram 2-n-pentyl-2-(2-ethylhexyl)-1 pack in 500 milliliters the flask that agitator, condenser, thermometer and airway are housed, ammediol, the tetrahydrofuran (THF) and 11 that adds 150 milliliters again restrains potassium tert.-butoxides, and this mixture was at room temperature stirred 30 minutes, the methyl iodide that dropwise adds 5 milliliters then, in this process, temperature is raised to 40 degree, reflux 5 hours voluntarily, and then adding 11 gram potassium tert.-butoxides, 5 milliliters of methyl iodide, reheat refluxed 6 hours.Reactant is filtered, and solvent is removed in the filtrate decompression distillation, and product is crossed column chromatography, gets product 7.5 grams.Nuclear magnetic data is as follows:
1HNMR (300MHz, CDCl
3, TMS is interior mark)
Can also make following compounds by changing component by the method for above-mentioned (a) and (b), (c)
2-methyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-ethyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-phenyl-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-allyl group-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-methyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-ethyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-benzyl-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-allyl group-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-methyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-ethyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-allyl group-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-methyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-ethyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-allyl group-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-methyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-ethyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-allyl group-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-methyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-ethyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-propyl group-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-isobutyl--2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-isopentyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-allyl group-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-methyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-ethyl-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-allyl group-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal.
Application test
Embodiment 2
With above-mentioned synthetic compound as follows, prepare olefins polymerizing solid catalyst component respectively.
In through the abundant metathetical reactor of high pure nitrogen, add magnesium chloride 4.8g successively, toluene 95ml, epoxy chloropropane 4ml, tributyl phosphate 12.5ml is warming up to 50 ℃ under stirring, and kept 2.5 hours, solid dissolves fully, adds Tetra hydro Phthalic anhydride 1.4g, continues to keep 1 hour.Solution is cooled to below-25 ℃, drips TiCl in 1 hour
456ml slowly is warming up to 80 ℃, separates out solids in temperature-rise period gradually, adds compound 2-n-pentyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal 6mmol, holding temperature 1 hour is after the filtration, add toluene 150ml, the washing secondary obtains solid sediment.Add toluene 100ml then, be warmed up to 110 ℃, carry out three washings, the time respectively is 10 minutes, adds hexane 60ml again, washed twice.Obtain ingredient of solid catalyst.The catalyst component of above-mentioned preparation is carried out propylene polymerization: volume is the stainless steel cauldron of 5L, after gaseous propylene is fully replaced, adds the AlEt of 0.5M
3Hexane solution 5ml, 0.02M methylcyclohexyl dimethoxy silane (CHMMS) hexane solution 5ml, add the solid ingredient 10mg and the 1.2L hydrogen of above-mentioned preparation again, feed liquid propene 2.5L, be warming up to 70 ℃, kept this temperature 1 hour, pressure is put in cooling, discharging gets the PP resin, calculate its activity, measure the degree of isotacticity and the molecular weight distributing index of resulting polymers, concrete outcome sees Table 1.
Embodiment 3-10 is with the preparation method of the solid catalyst of above-mentioned embodiment 2, and different is to adopt diether different in the general formula (I) as internal electron donor.
Comparative example 1 is with the preparation method of the solid catalyst of above-mentioned embodiment 2, and different is to adopt 2,2-diisobutyl-1,3-Propanal dimethyl acetal.
Comparative example 2 is with the preparation method of the solid catalyst of above-mentioned embodiment 2, and different is to adopt 2,2-diisoamyl-1,3-Propanal dimethyl acetal.
Table 1
From the data of table 1 as can be seen, adopt in the catalyst component of the present invention and be different from Chinese patent CN96107325.X and the disclosed diether compounds of CN89107675.1 as internal electron donor, after it is used for propylene polymerization, not only catalyst activity is higher, and resulting polymers molecular weight distribution broad, be suitable for developing the product of the multiple trade mark.
Claims (13)
1. the catalyst component that is used for olefinic polymerization, it includes magnesium, titanium, halogen and electron donor, and this electron donor is selected from least a in following general formula (I) diether compound:
In the formula: R is C
1～C
10Alkyl;
R
1Be a kind of C
1～C
7The primary alkyl of straight or branched, or H wherein randomly replaces by heteroatoms, and described heteroatoms is selected from F, Cl, Br or I;
R
2Be C
6～C
10Aryl, aralkyl or alkaryl or (R
3R
4)-CH-CH
2-group, wherein R
3, R
4Group, identical or different, be selected from C respectively
1～C
10Straight chained alkyl or H are wherein randomly replaced by a heteroatoms, and described heteroatoms is selected from F, Cl, Br or I, but R
3With R
4Not CH simultaneously
3Or R
3With R
4The formation cycloalkyl is connected with each other.
2. R is methyl or ethyl in the catalyst component that is used for olefinic polyreaction according to claim 1, general formula (I).
3. R in the catalyst component that is used for olefinic polyreaction according to claim 1, general formula (I)
1Be C
1～C
7The primary alkyl of straight or branched.
4. R in the catalyst component that is used for olefinic polyreaction according to claim 1, general formula (I)
2Be selected from phenyl, benzyl, 2-ethyl-butyl, 2-methyl butyl, 2-ethylhexyl, cyclopropyl methyl or cyclobutylmethyl.
5. the catalyst component that is used for olefinic polyreaction according to claim 1, general formula (I) is selected from following compound:
2-methyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-ethyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-phenyl-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-phenyl-1, the 3-Propanal dimethyl acetal;
2-methyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-ethyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-benzyl-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-benzyl-1, the 3-Propanal dimethyl acetal;
2-methyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-ethyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-(2-ethyl-butyl)-1, the 3-Propanal dimethyl acetal;
2-methyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-ethyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-(2-methyl butyl)-1, the 3-Propanal dimethyl acetal;
2-methyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-ethyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal;
2-methyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-ethyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-propyl group-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-isobutyl--2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-isopentyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-methyl-2-cyclopropyl methyl isophthalic acid, the 3-Propanal dimethyl acetal;
2-ethyl-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-propyl group-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-normal-butyl-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-n-pentyl-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-sec.-propyl-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-isobutyl--2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal;
2-isopentyl-2-cyclobutylmethyl-1, the 3-Propanal dimethyl acetal.
6. according to the described catalyst component that is used for olefinic polymerization of one of claim 1～5, it comprises titanium compound, magnesium compound and is selected from the reaction product of the diether compound of general formula (I), magnesium compound is selected from a kind of in one of them halogen atom alkoxy in the hydrate of magnesium dihalide, alkoxyl magnesium, alkyl magnesium, magnesium dihalide or alcohol adduct and the magnesium dihalide molecular formula or the halogenated alkoxy institute metathetical derivative or their mixture;
Titanium compound is that general formula is TiXn (OR)
4-n, R is that carbonatoms is 1～20 alkyl in the formula, X is a halogen, n=1～4.
7. the catalyst component that is used for olefinic polymerization according to claim 6, the magnesium compound that it adopted is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds.
8. the catalyst component that is used for olefinic polymerization according to claim 6, its organic epoxy compounds comprise at least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halo fat group alkene or diolefine of carbonatoms.
9. the catalyst component that is used for olefinic polymerization according to claim 6, its organo phosphorous compounds are the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.
10. the catalyst component that is used for olefinic polymerization according to claim 6, the magnesium compound that it adopted is the alcohol adduct of magnesium dihalide.
11. one kind is used for CH
2The catalyzer of=CHR olefinic polyreaction, wherein R is hydrogen or C
1～C
6Alkyl or aryl, comprise the reaction product of following component:
(1) the described catalyst component of one of claim 1～10;
(2) alkylaluminium cpd;
(3) randomly, external electron donor component.
12. one kind is used for alkene CH
2=CHR polymeric pre-polymerized catalyst, wherein R is hydrogen or C
1～C
6Alkyl group, described pre-polymerized catalyst comprises and a kind ofly carries out the prepolymer of prepolymerization gained according to catalyzer described in the claim 11 and alkene, the pre-polymerization multiple is 0.1～1000g olefin polymer/g ingredient of solid catalyst.
13. be used for alkene CH
2=CHR polymeric method, wherein R is the hydrocarbyl group of hydrogen or 1～6 carbon atom, carries out in the presence of claim 11 or 12 described catalyzer or pre-polymerized catalyst.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107344976A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | Catalytic component, catalyst system and its application for olefinic polymerization |
| CN107629156A (en) * | 2016-07-18 | 2018-01-26 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and the catalyst for olefinic polymerization and its application |
| CN109422834A (en) * | 2017-09-05 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of low VOC, high just high flow polypropylene and preparation method thereof |
-
2009
- 2009-10-23 CN CN 200910236267 patent/CN102040684A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107344976A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | Catalytic component, catalyst system and its application for olefinic polymerization |
| CN107344976B (en) * | 2016-05-05 | 2021-03-16 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst system and application thereof |
| CN107629156A (en) * | 2016-07-18 | 2018-01-26 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and the catalyst for olefinic polymerization and its application |
| CN107629156B (en) * | 2016-07-18 | 2020-05-12 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst for olefin polymerization and application thereof |
| CN109422834A (en) * | 2017-09-05 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of low VOC, high just high flow polypropylene and preparation method thereof |
| CN109422834B (en) * | 2017-09-05 | 2021-07-30 | 中国石油化工股份有限公司 | Low-VOC (volatile organic compound), high-rigidity and high-fluidity polypropylene and preparation method thereof |
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