CN101125896B - Catalyst component used for olefin polymerization reaction and its catalyst - Google Patents
Catalyst component used for olefin polymerization reaction and its catalyst Download PDFInfo
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- CN101125896B CN101125896B CN2006101124454A CN200610112445A CN101125896B CN 101125896 B CN101125896 B CN 101125896B CN 2006101124454 A CN2006101124454 A CN 2006101124454A CN 200610112445 A CN200610112445 A CN 200610112445A CN 101125896 B CN101125896 B CN 101125896B
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Abstract
The invention provides a catalyst components used in CH2=CHR olefin polymerization reaction and the catalyst thereof, wherein R is hydrogen or C1-C6 alkyl or aryl group. The catalyst components comprise magnesium, titanium, halogens and electron donor. The electron donor is at least a piperidine compound in the general formula (I): wherein: R1 is C1-C6 straight chain or branched chain alkyl, or C6-C20 aryl group or alkaryl; R' is hydrogen or C1-C6 straight chain or branched chain alkyl, or C6-C20 aryl group or alkaryl, or is acyl in OCOR 10; R2-R9 is the same or different and is hydrogen or C1-6 straight chain or branched chain alkyl, C6-C20 aryl group or alkaryl. Satisfying polymeric producing ratio can be obtained when the catalyst is used in propylene polymerization and the polymer hascomparatively high stereospecificity that is good for developing different numbers of polymer.
Description
Technical field
The present invention relates to a kind of ingredient of solid catalyst that contains the piperidines 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 CN1042547A and the disclosed catalyst component that is used for olefinic polyreaction of CN1143651A, special 1 of two ether groups that contain have been adopted, 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.At the disclosed ingredient of solid catalyst that is used for olefinic polyreaction of Chinese patent CN1054139A, adopted special 1 of two ketone groups that contain, the 3-cyclohexadione compounds is as electron donor, for example 2,2,4,6,6-pentamethyl--3,5-heptadione and 2,2,6,6-tetramethyl--4-3,5-heptadione etc.
The special dibasic aliphatic carboxylic acid ester compound of one class is disclosed again recently, as (referring to WO98/56830, WO98/56834, WO01/57099, WO01/63231 and WO00/55215) such as succinate, malonic ester, glutarates, the use of this class electron donor compound not only can improve activity of such catalysts, and the molecular weight distribution of gained propene polymer is obviously widened.
Yet, above-mentioned disclosed catalyzer also exists some not satisfied defective in the practical application of olefinic polymerization, the inventor unexpectedly finds, in olefin polymerization catalysis by using a kind of new piperidines 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, and the stereospecificity of polymkeric substance is higher, catalyzer has better hydrogen regulation sensitivity simultaneously, and is 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 piperidines in the following general formula (I):
In the formula: R
1Be C
1～C
6The alkyl of straight or branched or C
6～C
20Aryl or alkaryl; R ' is hydrogen or C
1～C
6The alkyl or the C of straight or branched
6～C
20Aryl or aralkyl or as OCO R
10Shown acyl group; R
2～R
9Identical or different, be hydrogen or C
1-6Alkyl, the C of straight or branched
6～C
20Aryl or aralkyl.
Preferably, R in the general formula (I)
1Be C
3～C
6The alkyl of straight or branched or C
6～C
20Aryl.Particularly, R
1Be selected from methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or phenyl.
Preferably, R ' is hydrogen or C in the general formula (I)
1～C
6The alkyl or the C of straight or branched
6～C
10Aryl or aralkyl; Particularly, R ' can be selected from hydrogen, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, phenyl, benzyl.
R ' is also as OCOR in the general formula (I)
10Shown acyl group, wherein R
10Be C
3～C
6The alkyl of straight or branched or C
6～C
20Aryl.Particularly, R
10Can be selected from methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or phenyl.
Preferably, R in the general formula (I)
2, R
3, R
6And R
7Identical or different, be C
1～C
4The alkyl of straight or branched.
The specific examples of substituted piperidines of the present invention comprises:
2,2,6,6-tetramethyl--4-benzoyloxy piperidines,
2,2,6,6-tetramethyl--4-acetoxyl group piperidines,
2,2,6,6-tetramethyl--4-propionyloxy piperidines,
2,2,6,6-tetramethyl--4-butyryl acyloxy piperidines,
2,2,6, the different propionyloxy piperidines of 6-tetramethyl--4-,
2,2,6,6-tetramethyl--4-benzoyloxy-N-methyl piperidine,
2,2,6,6-tetramethyl--4-benzoyloxy-N-ethylpiperidine,
2,2,6,6-tetramethyl--4-benzoyloxy-N-propyl group piperidines,
2,2,6,6-tetramethyl--4-benzoyloxy-N-sec.-propyl piperidines,
2,2,6,6-tetramethyl--4-benzoyloxy-N-butyl piperidine,
2,2,6,6-tetramethyl--4-benzoyloxy-N-benzyl piepridine,
2,2,6,6-tetramethyl--4-butyryl acyloxy-N-methyl piperidine,
2,2,6,6-tetramethyl--4-butyryl acyloxy-N-ethylpiperidine,
2,2,6,6-tetramethyl--4-acetoxyl group-N-methyl piperidine,
2,2,6,6-tetramethyl--4-propionyloxy-N-methyl piperidine,
2,2,6, the different propionyloxy of 6-tetramethyl--4--N-methyl piperidine,
2,2,6,6-tetramethyl--4-propionyloxy-N-propionyl piperidines,
2,2,6, the different propionyl piperidines of the different propionyloxy-N-of 6-tetramethyl--4-,
2,2,6,6-tetramethyl--4-isobutyl acyloxy-N-methyl piperidine,
2,2,6,6-tetramethyl--4-isobutyl acyloxy-N-ethylpiperidine,
2,2,6,6-tetramethyl--4-isobutyl acyloxy-N-propyl group piperidines,
2,2,6,6-tetramethyl--4-butyryl acyloxy-N-butyryl radicals piperidines,
2,2,6,6-tetramethyl--4-butyryl acyloxy-N-methyl piperidine,
2,2,6,6-tetramethyl--4-butyryl acyloxy-N-butyl piperidine,
2,2,6,6-tetramethyl--4-butyryl acyloxy-N-methyl piperidine,
2,2,6,6-tetramethyl--4-isobutyl acyloxy-N-isobutyryl piperidines.
Piperidines of the present invention can prepare as follows:
Under alkaline condition, with general formula (II) and R
1COC1 carries out obtaining product after the acylation reaction, or earlier with general formula (II) and R
1COCl carries out obtaining product, R in its formula of (II) with R ' X or R ' COCl reaction again after the acylation reaction
1～R
9And R ' is as the definition in the general formula (I), and X is a halogen:
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 piperidines 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 piperidines 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 piperidines 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 chloride 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 piperidines 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 ingredient of solid catalyst that contains magnesium, titanium, halogen and be selected from the piperidines of general formula (I);
(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 and R
Be of the same race or different alkyl, cycloalkyl, aryl, haloalkyl, 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 by adopting novel internal electron donor piperidines, can obtain the catalyzer of high comprehensive performance, when being used for propylene polymerization, can obtain gratifying polymerization yield rate.And adopt method can obtain different catalizer varieties by the different internal electron donor compounds of conversion, and directly regulate the degree of isotacticity of resulting polymers by the gained catalyzer, be suitable for the development research of the multiple product trade mark.
Embodiment
Embodiment given below is for the present invention is described, rather than limits the invention.
Testing method:
1, fusing point: adopt XT4A micro melting point apparatus (temperature control type).
2, 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).
3, 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.
4, melting index is to measure according to ASTM D1238-99.
One, compound is synthetic:
Embodiment 12, and 2,6,6-tetramethyl--4-benzoyloxy-N-benzoyl piperidines synthetic
Be equipped with in the reaction flask of whipping appts and reflux condensing tube one and add 2,2,6,6-tetramethyl--4-hydroxy piperidine (4.0g), sodium bicarbonate (2.5g), tetrahydrofuran (THF) (50ml) is added dropwise to Benzoyl chloride (4ml) and tetrahydrofuran (THF) (15ml) under stirring.Added the back room temperature reaction 2 hours, heating reflux reaction 6 hours.Reaction finishes the back cooling, adds the entry dilution, and extracted with diethyl ether three times merges organic phase.With washing with saturated nacl aqueous solution after 40 ℃ the water washing, the organic phase anhydrous magnesium sulfate drying spends the night again.Remove and obtain product 2,2,6,6-tetramethyl--4-benzoyloxy-N-benzoyl piperidines after column chromatography is crossed in the back of desolvating.
1H-NMR(δ，ppm，TMS，CDCl
3)：8.0～8.1(4H，m，ArH)，7.5～7.7(2H，m，ArH)，7.2～7.5(4H，m，ArH)，4.3(1H，m，OCH)，1.7～1.9(4H，m，CH
2)，1.2～1.4(12H，d，CH
3)。
Embodiment 22, and 2,6,6-tetramethyl--4-butyryl acyloxy-N-butyryl radicals piperidines synthetic
In a reaction flask that whipping appts and reflux condensing tube be housed, add 2,2,6,6-tetramethyl--4-hydroxy piperidine (3.14g), sodium bicarbonate (10g), tetrahydrofuran (THF) (50ml) is added dropwise to n-butyryl chloride (4.2ml) and tetrahydrofuran (THF) (25ml) under stirring.Added the back room temperature reaction 2 hours, heating reflux reaction 6 hours.Reaction finishes the back cooling, adds the entry dilution, and extracted with diethyl ether three times merges organic phase.With washing with saturated nacl aqueous solution after 40 ℃ the water washing, the organic phase anhydrous magnesium sulfate drying spends the night again.Remove and obtain product 2,2,6,6-tetramethyl--4-butyryl acyloxy-N-butyryl radicals piperidines after column chromatography is crossed in the back of desolvating.
1H-NMR(δ，ppm，TMS，CDCl
3)：4.3(1H，m，OCH)，3.6～3.7(4H，m，CH)，2.2～2.4(4H，m，CH
2)，1.8～1.9(4H，m，CH
2)，1.6～1.8(6H，m，CH
3)，0.8～1.0(12H，s，CH
3)。
Embodiment 32, and 2,6,6-tetramethyl--4-isobutyl acyloxy-N-isobutyryl piperidines synthetic
In a reaction flask that whipping appts and reflux condensing tube be housed, add 2,2,6,6-tetramethyl--4-hydroxy piperidine (3.14g), sodium bicarbonate (10g), tetrahydrofuran (THF) (50ml) is added dropwise to isobutyryl chloride (4.2ml) and tetrahydrofuran (THF) (25ml) under stirring.Added the back room temperature reaction 2 hours, heating reflux reaction 6 hours.Reaction finishes the back cooling, adds the entry dilution, and extracted with diethyl ether three times merges organic phase.With washing with saturated nacl aqueous solution after 40 ℃ the water washing, the organic phase anhydrous magnesium sulfate drying spends the night again.Remove and obtain product 2,2,6,6-tetramethyl--4-isobutyl acyloxy-N-isobutyryl piperidines after column chromatography is crossed in the back of desolvating.
1H-NMR(δ，ppm，TMS，CDCl
3)：4.1(1H，m，OCH)，3.6～3.7(4H，m，CH)，2.5～2.6(H，m，CH)，1.8～1.9(6H，m，CH
3)，1.1～1.3(12H，s，CH
3)。
Embodiment 42, and 2,6,6-tetramethyl--4-isobutyl acyloxy-N-methyl piperidine synthetic
In a reaction flask that whipping appts and reflux condensing tube be housed, add 2,2,6,6-tetramethyl--4-hydroxy-n-methyl piperidine (3.42g), sodium bicarbonate (10g), tetrahydrofuran (THF) (50ml) is added dropwise to isobutyryl chloride (4.2ml) and tetrahydrofuran (THF) (25ml) under stirring.Added the back room temperature reaction 2 hours, heating reflux reaction 6 hours.Reaction finishes the back cooling, adds the entry dilution, and extracted with diethyl ether three times merges organic phase.With washing with saturated nacl aqueous solution after 40 ℃ the water washing, the organic phase anhydrous magnesium sulfate drying spends the night again.Remove and obtain product 2,2,6,6-tetramethyl--4-isobutyl acyloxy-N-methyl piperidine after column chromatography is crossed in the back of desolvating.
1H-NMR(δ，ppm，TMS，CDCl
3)：4.1(1H，m，OCH)，3.6～3.7(4H，m，CH)，2.5～2.6(H，m，CH)，2.1～2.2(3H，s，CH
3)，1.8～1.9(3H，m，CH
3)，1.1～1.3(12H，s，CH
3)。
Embodiment 52, and 2,6,6-tetramethyl--4-butyryl acyloxy-N-methyl piperidine synthetic
Be equipped with in the reaction flask of whipping appts and reflux condensing tube one and add 2,2,6,6-tetramethyl--4-hydroxy-n-methyl piperidine (3.42g), sodium bicarbonate (10g), tetrahydrofuran (THF) (50ml) is added dropwise to butyryl chloride (4.2ml) and tetrahydrofuran (THF) (25ml) under stirring.Added the back room temperature reaction 2 hours, heating reflux reaction 6 hours.Reaction finishes the back cooling, adds the entry dilution, and extracted with diethyl ether three times merges organic phase.With washing with saturated nacl aqueous solution after 40 ℃ the water washing, the organic phase anhydrous magnesium sulfate drying spends the night again.Remove and obtain product 2,2,6,6-tetramethyl-4-butyryl acyloxy-N-methyl piperidine after column chromatography is crossed in the back of desolvating.
1H-NMR(δ，ppm，TMS，CDCl
3)：4.1(1H，m，OCH)，3.6～3.7(4H，m，CH)，2.3(2H，m，CH
2)，2.1～2.2(3H，s，CH
3)，1.6～1.8(2H，m，CH
2)，1.2～1.4(3H，m，CH
3)，0.9～1.0(12H，s，CH
3)。
Embodiment 62, and 2,6,6-tetramethyl--4-benzoyloxy piperidines synthetic
In a reaction flask that whipping appts and reflux condensing tube be housed, add 2,2,6,6-tetramethyl--4-hydroxy piperidine (3.14g), sodium bicarbonate (10g), tetrahydrofuran (THF) (50ml) is added dropwise to Benzoyl chloride (2.1ml) and tetrahydrofuran (THF) (25ml) under stirring.Added the back room temperature reaction 2 hours, heating reflux reaction 6 hours.Reaction finishes the back cooling, adds the entry dilution, and extracted with diethyl ether three times merges organic phase.With washing with saturated nacl aqueous solution after 40 ℃ the water washing, the organic phase anhydrous magnesium sulfate drying spends the night again.Remove and obtain product 2,2,6,6-tetramethyl--4-benzoyloxy piperidines after column chromatography is crossed in the back of desolvating.
1H-NMR(δ，ppm，TMS，CDCl
3)：8.0～8.1(4H，d，ArH)，7.5～7.6(2H，m，ArH)，7.4～7.5(4H，m，ArH)，2.8～3.1(4H，s，CH)，1.8～2.0(4H，s，NH)，1.1～1.5(4H，m，CH
2)，0.7～0.8(12H，m，CH
3)。
Embodiment 72, and 2,6,6-tetramethyl--4-benzoyloxy-N-benzyl piepridine synthetic
One whipping appts and reflux condensing tube are housed, be filled with the tetrahydrofuran (THF) that adds sodium hydride 0.8g and 50 milliliters in the reaction flask of nitrogen, be added dropwise to 4.5g the foregoing description 6 synthetic 2 under stirring, 2,6, the mixing solutions of 6-tetramethyl--4-benzoyloxy piperidines and 20 milliliters of tetrahydrofuran (THF)s, control reaction temperature be at 0～10 ℃, drips back stirring reaction 4 hours under room temperature.Cool to 0～10 ℃ after having reacted, stir the mixing solutions that drips 7.8 milliliters of benzyl chlorides and 25 milliliters of tetrahydrofuran (THF)s down, dripped afterwards under room temperature stirring reaction 4 hours, be warming up to back flow reaction 4 hours in low temperature.Reaction finishes the back cooling, adds 50 milliliters of ether, adds saturated aqueous ammonium chloride solution again, stirring reaction 0.5 hour.Tell organic phase, use the extracted with diethyl ether water, merge organic phase, with 20 ml waters and 20 milliliters of saturated nacl aqueous solution washing organic phases, spend the night with anhydrous magnesium sulfate drying then successively.Obtain crude product except that after desolvating, tell product 2,2,6,6-tetramethyl--4-benzoyloxy-N-benzyl piepridine through column chromatography.
1H-NMR(δ，ppm，TMS，CDCl
3)：8.0～8.1(4H，d，ArH)，7.5～7.6(2H，m，ArH)，7.4～7.5(4H，m，ArH)，2.6～3.1(1H，m，CH)，2.1～2.2(2H，s，CH
2)，1.1～1.5(4H，m，CH)，0.7～0.8(12H，m，CH
3)。
Embodiment 82, and 2,6,6-tetramethyl--4-benzoyloxy-N-methyl piperidine synthetic
At one whipping appts and reflux condensing tube are housed, are filled with in the reaction flask of nitrogen and add sodium bicarbonate (8g), tetrahydrofuran (THF) (50ml), 2,2,6,6-tetramethyl--4-hydroxy-n-methyl piperidine (4.0g) is added dropwise under stirring
The benzene firstAcyl chlorides (2.1ml) and tetrahydrofuran (THF) (25ml).Added the back room temperature reaction 2 hours, heating reflux reaction 6 hours.Reaction finishes the back cooling, adds the entry dilution, tells organic phase, and extracted with diethyl ether three times merges organic phase.With washing with saturated nacl aqueous solution after 40 ℃ the water washing, the organic phase anhydrous magnesium sulfate drying spends the night again.Remove and obtain product 2,2,6,6-tetramethyl--4-benzoyloxy-N-methyl piperidine after column chromatography is crossed in the back of desolvating.
1H-NMR(δ，ppm，TMS，CDCl
3)：8.0～8.1(4H，d，ArH)，7.5～7.6(2H，m，ArH)，7.4～7.5(4H，m，ArH)，2.8～3.1(1H，m，CH)，2.1～2.2(3H，s，NCH
3)，1.1～1.5(4H，m，CH
2)，0.7～0.8(12H，m，CH
3)。
Application test
1, with above-mentioned synthetic compound as follows, prepares 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 preparation embodiment synthetic piperidines 6mmol respectively, and holding temperature 1 hour after the filtration, adds toluene 150ml, and 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.
2, the catalyst component with above-mentioned preparation carries out propylene polymerization:
Volume is the stainless steel cauldron of 5L, after gaseous propylene is fully replaced, adds AlEt
32.5ml, methylcyclohexyl dimethoxy silane (CHMMS) 5ml makes Al/Si (mol)=25, adds the solid ingredient 10mg and the 1.2L hydrogen of above-mentioned preparation again, feeds 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 melting index of resulting polymers, concrete outcome sees Table 1.
Embodiment 9 is with the preparation method of above-mentioned solid catalyst, just the consumption with the piperidines of embodiment 6 changes 4mmol into, the solid catalyst that obtains, examine by above-mentioned polymerization process, catalyst activity 25.3kgPP/gcat, the polymkeric substance degree of isotacticity is 97.3, and melt index is 2.9g/10min.
Embodiment 10 examines the solid catalyst that embodiment 6 obtains by above-mentioned polymerization process, just amounts of hydrogen changes 6.0L into, and obtaining activity of such catalysts is 28.2kgPP/gcat, and melt index is 47.6g/10min.
Table 1
| Embodiment | Piperidines | Active (kg polymkeric substance/g catalyzer) | MI (g/10min) | Degree of isotacticity (%) |
| Example 1 | 2,2,6,6-tetramethyl--4-benzoyloxy-N-benzoyl piperidines | 10.6 | 3.7 | 93.3 |
| Example 2 | 2,2,6,6-tetramethyl--4-butyryl acyloxy-N-butyryl radicals piperidines | 13.1 | 1.6 | 96.3 |
| Example 3 | 2,2,6,6-tetramethyl--4-isobutyl acyloxy-N-isobutyryl piperidines | 13.2 | 3.1 | 95.2 |
| Example 4 | 2,2,6,6-tetramethyl--4-isobutyl acyloxy-N-methyl piperidine | 14.0 | 3.1 | 96.3 |
| Example 5 | 2,2,6,6-tetramethyl--4-butyryl acyloxy-N-methyl piperidine | 11.4 | 2.5 | 94.0 |
| Example 6 | 2,2,6,6-tetramethyl--4-benzoyloxy piperidines | 20.4 | 2.1 | 97.6 |
| Example 7 | 2,2,6,6-tetramethyl--4-benzoyloxy-N benzyl piepridine | 23.3 | 2.0 | 94.7 |
| Example 8 | 2,2,6,6-tetramethyl--4-benzoyloxy-N methyl piperidine | 15.9 | 6.5 | 97.2 |
| Example 9 | 2,2,6,6-tetramethyl--4-benzoyloxy piperidines | 25.3 | 2.9 | 97.3 |
| Example 10 | 2,2,6,6-tetramethyl--4-benzoyloxy piperidines | 28.2 | 47.6 |
From the data of table 1 as can be seen, after catalyst component of the present invention is used for propylene polymerization, not only catalyst activity is higher, and the degree of isotacticity of polymkeric substance is also higher, and can directly regulate the degree of isotacticity of resulting polymers by the variation of piperidines kind, be suitable for developing the product of the multiple trade mark.
Claims (14)
1. the catalyst component that is used for propylene polymerization, it comprises titanium compound, magnesium compound and is selected from the reaction product of at least a piperidines in the general formula (I),
Magnesium compound is selected from the hydrate or the alcohol adduct of magnesium dihalide, magnesium dihalide,
Titanium compound is that general formula is TiX
n(OR)
4-n, R is that carbonatoms is 1～20 alkyl in the formula, X is a halogen, and n=1～4,
In the formula: R
1Be C
1～C
6The alkyl of straight or branched or C
6～C
20Aryl or alkaryl; R ' is hydrogen or C
1～C
6The alkyl or the C of straight or branched
6～C
20Aryl or aralkyl or as COR
10Shown acyl group, R
10Be C
3～C
6The alkyl of straight or branched or C
6～C
20Aryl; R
2～R
9Identical or different, be hydrogen or C
1-6Alkyl, the C of straight or branched
6～C
20Aryl or aralkyl.
2. R in the catalyst component that is used for propylene polymerization according to claim 1, general formula (I)
1Be C
3～C
6The alkyl of straight or branched or C
6～C
20Aryl.
3. R in the catalyst component that is used for propylene polymerization according to claim 1, general formula (I)
1Be phenyl or butyl.
4. R in the catalyst component that is used for propylene polymerization according to claim 1, general formula (I)
1It is isobutyl-.
5. R ' is hydrogen or C in the catalyst component that is used for propylene polymerization according to claim 1, general formula (I)
1～C
6The alkyl or the C of straight or branched
6～C
10Aryl or aralkyl.
6. R ' is as COR in the catalyst component that is used for propylene polymerization according to claim 1, general formula (I)
10Shown acyl group, wherein R
10Be C
3～C
6The alkyl of straight or branched or C
6～C
20Aryl.
7. the catalyst component that is used for propylene polymerization according to claim 1, general formula (I) is selected from following compound:
2,2,6,6-tetramethyl--4-benzoyloxy piperidines,
2,2,6,6-tetramethyl--4-acetoxyl group piperidines,
2,2,6,6-tetramethyl--4-propionyloxy piperidines,
2,2,6,6-tetramethyl--4-butyryl acyloxy piperidines,
2,2,6,6-tetramethyl--4-benzoyloxy-N-methyl piperidine,
2,2,6,6-tetramethyl--4-benzoyloxy-N-ethylpiperidine,
2,2,6,6-tetramethyl--4-benzoyloxy-N-propyl group piperidines,
2,2,6,6-tetramethyl--4-benzoyloxy-N-sec.-propyl piperidines,
2,2,6,6-tetramethyl--4-benzoyloxy-N-butyl piperidine,
2,2,6,6-tetramethyl--4-benzoyloxy-N-benzyl piepridine,
2,2,6,6-tetramethyl--4-butyryl acyloxy-N-methyl piperidine,
2,2,6,6-tetramethyl--4-butyryl acyloxy-N-ethylpiperidine,
2,2,6,6-tetramethyl--4-acetoxyl group-N-methyl piperidine,
2,2,6,6-tetramethyl--4-propionyloxy-N-methyl piperidine,
2,2,6,6-tetramethyl--4-propionyloxy-N-propionyl piperidines,
2,2,6,6-tetramethyl--4-isobutyl acyloxy-N-methyl piperidine,
2,2,6,6-tetramethyl--4-isobutyl acyloxy-N-ethylpiperidine,
2,2,6,6-tetramethyl--4-isobutyl acyloxy-N-propyl group piperidines,
2,2,6,6-tetramethyl--4-butyryl acyloxy-N-butyryl radicals piperidines,
2,2,6,6-tetramethyl--4-butyryl acyloxy-N-butyl piperidine,
2,2,6,6-tetramethyl--4-isobutyl acyloxy-N-isobutyryl piperidines.
8. the catalyst component that is used for propylene polymerization according to claim 1, the magnesium compound that it adopted is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds.
9. the catalyst component that is used for propylene polymerization according to claim 8, its organic epoxy compounds comprise at least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halogenated aliphatic alkene or diolefine of carbonatoms.
10. the catalyst component that is used for propylene polymerization according to claim 8, its organo phosphorous compounds are the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.
11. the catalyst component that is used for propylene polymerization according to claim 1, the magnesium compound that it adopted is the alcohol adduct of magnesium dihalide.
12. a catalyzer that is used for propylene polymerization comprises the reaction product of following component:
(1) the described catalyst component of one of claim 1～11;
(2) alkylaluminium cpd;
(3) randomly, external electron donor component.
13. pre-polymerized catalyst that is used for propylene polymerization, described pre-polymerized catalyst comprises and a kind ofly carries out the prepolymer of prepolymerization gained according to catalyzer described in the claim 12 and alkene, and the pre-polymerization multiple is 0.1～1000g olefin polymer/g ingredient of solid catalyst.
14. be used for the method for propylene polymerization, in the presence of described catalyzer of claim 12 or 13 described pre-polymerized catalysts, carry out.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100997A (en) * | 1985-04-01 | 1987-01-10 | 化工部北京化工研究院 | The catalyst system that is used for olefinic polymerization and copolymerization |
| CN1039606A (en) * | 1988-06-30 | 1990-02-14 | 希巴-盖吉股份公司 | The method for preparing heat-stable olefin polymers |
| CN1152582A (en) * | 1995-10-16 | 1997-06-25 | 住友化学工业株式会社 | Method for preparing catalyst component for olefin polymerization, catalyst for olefin polymerization and process for producing olefin polymer with catalyst |
-
2006
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100997A (en) * | 1985-04-01 | 1987-01-10 | 化工部北京化工研究院 | The catalyst system that is used for olefinic polymerization and copolymerization |
| CN1039606A (en) * | 1988-06-30 | 1990-02-14 | 希巴-盖吉股份公司 | The method for preparing heat-stable olefin polymers |
| CN1152582A (en) * | 1995-10-16 | 1997-06-25 | 住友化学工业株式会社 | Method for preparing catalyst component for olefin polymerization, catalyst for olefin polymerization and process for producing olefin polymer with catalyst |
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| Title |
|---|
| JP特开平6-41228A 1994.02.15 |
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