CN102040679A - Catalyst component and catalyst for olefinic polymerization reaction - Google Patents
Catalyst component and catalyst for olefinic polymerization reaction Download PDFInfo
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- CN102040679A CN102040679A CN2009102355604A CN200910235560A CN102040679A CN 102040679 A CN102040679 A CN 102040679A CN 2009102355604 A CN2009102355604 A CN 2009102355604A CN 200910235560 A CN200910235560 A CN 200910235560A CN 102040679 A CN102040679 A CN 102040679A
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Abstract
The invention provides a catalyst component for CH2=CHR olefinic polymerization reaction, wherein R is hydrogen or C1-C6 alkyl group or aryl group. The catalyst component comprises magnesium, titanium, halogen and electron donor, wherein the electron donor is selected from at least one compound in the general formula (I); R1 and R2 can be identical or different, and can respectively be a C1-C10 straight-chain or branch-chain alkyl group or naphthenic group, or C5-C20 aryl group or aralkyl group; and R3, R4 and R5 can be identical or different, and can respectively be a C1-C10 straight-chain or branch-chain alkyl group or alkoxy group, C5-C15 aryl group or aralkyl group, hydrogen, halogen, acyl group, ester group, amido group or amino group.
Description
Technical field
The present invention relates to a kind of ingredient of solid catalyst of the compound of specific functional groups ketone group and alkyd ester group, the catalyzer that contains this ingredient of solid catalyst and this catalyzer of containing at CH
2Application in the=CHR olefinic polyreaction, wherein R is hydrogen or C
1-C
6Alkyl or aryl, when particularly being applied to propylene polymerization, this catalyzer has very high activity and good taxis, and hydrogen response is good, the gained acrylic resin has wider molecular weight distribution, the high comprehensive performance of catalyzer.
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, the electron donor that people attempt to adopt other compound to be used as in the olefin polymerization catalyst components again uses, 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, this class electron donor compound can make the molecular weight distribution of propene polymer obviously widen.
Yet above-mentioned disclosed catalyzer also exists some not satisfied defective in the practical application of olefinic polymerization.For example adopt the catalytic activity of catalyzer of binary aromatic carboxylic acid's compounds lower, and the molecular weight distribution of resulting polymers is also narrower; Adopt 1, though the catalyzer of 3-diether compound is active higher, the hydrogen response of catalyzer, the narrow molecular weight distribution of resulting polymers is unfavorable for the exploitation of the different trades mark of polymkeric substance; And adopt the catalyst activity of recent disclosed dibasic aliphatic carboxylicesters still on the low side.
The inventor finds by a large amount of tests, in olefin polymerization catalysis by using a kind of new compound that contains particular functional group's ketone group and alkyd ester group as electron donor, can obtain the catalyzer of high comprehensive performance, when being used for propylene polymerization, this catalyzer has very high activity and good taxis, and hydrogen response is good, and the gained acrylic resin has wider molecular weight distribution, the high comprehensive performance of catalyzer.
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 compound in the following general formula (I):
In the compound of general formula (I): R
1, R
2Can be identical or inequality, be C
1～C
10Alkyl or cycloalkyl, the C of straight or branched
5～C
20Aryl or aralkyl, preferred R
1, R
2Be C
1～C
6Alkyl or cycloalkyl, the C of straight or branched
5～C
20Aryl or aralkyl, more preferably R
1, R
2Be C
5～C
20Aryl, especially preferred R
1, R
2Be phenyl; R
3, R
4, R
5Can be identical or inequality, be C
1～C
10The alkyl of straight or branched or alkoxyl group, C
5～C
20Aryl or aralkyl, hydrogen, halogen, acyl group, ester group, amide group or amino, preferred R
3, R
4, R
5Be C
1～C
8The alkyl of straight or branched or alkoxyl group, C
5～C
15Aryl or aralkyl, hydrogen, halogen, acyl group, ester group or amide group, more preferably R
3, R
4, R
5Be hydrogen, halogen or ester group.
In the compound of general formula (I), phenyl ring can be replaced by naphthalene nucleus or other condensed ring.
Above-claimed cpd can prepare by the following method: in the presence of lewis acid catalyst, aromatics is carried out electrophilic substitution reaction, obtain the aromatic series phenolic compound that corresponding ketone group replaces, carry out esterification by above-claimed cpd with corresponding acyl chlorides and obtain final product.Synthetic " practical organic chemistry handbook (Shanghai science tech publishing house) chapter 5 (237-277 page or leaf) that mainly compiles of compound with reference to Li Shuwen, Fan Rulin.
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 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 halogenated aliphatic 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 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 compound, and 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, and titanium compound is 0.5～150 mole, and the 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 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 and 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, kept 0.1～2 hour, carry out reaction with titanium compound.TiCl
4Processing can be carried out once or repeatedly.Using TiCl
4Can add above-mentioned general formula ammonia ester 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 ingredient of solid catalyst that contains magnesium, titanium, halogen and be selected from the compound 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 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.
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: 0～150 ℃ of polymerization temperature, preferred 60～90 ℃.
Catalyzer of the present invention can directly add and be used for polymerization process in the reactor.Perhaps, catalyzer can carry out prepolymerization before adding first polymerization reactor.In the present invention, " pre-polymerized catalyst " refers to 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 its surplus to be up to one or more alpha-olefins of 20mol% carries out prepolymerization.Preferably, the transforming degree of pre-polymerized catalyst components is about 0.2～500 gram polymkeric substance/gram ingredient 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 compound, can obtain the catalyzer of high comprehensive performance, when being used for propylene polymerization, this catalyzer has higher activity, hydrogen response is good, the gained acrylic resin has wider molecular weight distribution, the high comprehensive performance of catalyzer.
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. polymkeric substance isotactic index II: adopt 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 isotactic index with 2 ratio.
4. melting index MI: use fusion index instrument under 230 ℃, 2.16kg pressure, measure according to ASTM D1238-99 " measuring the standard test methods of thermoplasticity fusing flow rate with the extruding plastometer ".
5. polymericular weight and molecular weight distribution: adopt the Waters Waters Alliance GPC2000 of company gel permeation chromatograph to measure, 1,2, the 4-trichlorobenzene is a solvent, vinylbenzene is standard specimen.
One, compound is synthetic:
Synthesizing of embodiment 1 compound 2-benzoyloxy benzophenone
In the reaction flask of a 250ml, after nitrogen blows row, add 2-benzoyl phenol (5.0g, 0.025mol), tetrahydrofuran (THF) (50ml) and triethylamine (7.1ml, 0.05mol), stir cooling down the dropping Benzoyl chloride (5.9ml, 0.05mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains the light yellow slightly cementation body of product 6.5g, productive rate 86%.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.30～8.16(14H，m，ArH)。
Synthesizing of embodiment 2 compound 3-benzoyloxy benzophenone
In the reaction flask of a 250ml, after nitrogen blows row, add 3-benzoyl phenol (5.0g, 0.025mol), tetrahydrofuran (THF) (50ml) and triethylamine (7.1ml, 0.05mol), stir cooling down the dropping Benzoyl chloride (5.9ml, 0.05mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product white solid 6.8g, productive rate 89%, mp=67～69 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.47～8.24(14H，m，ArH)。
Synthesizing of embodiment 3 compound 4-benzoyloxy benzophenone
In the reaction flask of a 250ml, after nitrogen blows row, add 4-benzoyl phenol (5.0g, 0.025mol), tetrahydrofuran (THF) (50ml) and triethylamine (7.1ml, 0.05mol), stir cooling down the dropping Benzoyl chloride (5.9ml, 0.05mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product white plates crystal 7.0g, productive rate 92%, mp=109～111 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.36～8.26(14H，m，ArH)。
Embodiment 4 compounds 2 '-benzoyloxy Propiophenone synthetic
In the reaction flask of a 250ml, after nitrogen blows row, add 2-propionyl phenol (3.8g, 0.025mol), tetrahydrofuran (THF) (50ml) and triethylamine (7.1ml, 0.05mol), stir cooling down the dropping Benzoyl chloride (5.9ml, 0.05mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains the light yellow slightly cementation body of product 5.8g, productive rate 91%.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.22～8.23(9H，m，ArH)，2.88～2.95(2H，m，CH
2)，1.10～1.15(3H，t，CH
3)。
Embodiment 5 compounds 2 ', 4 '-dibenzoyl oxygen base Propiophenone synthetic
In the reaction flask of a 250ml, after nitrogen blows row, add 4-propionyl 1, the 3-dihydroxy-benzene (4.2g, 0.025mol), tetrahydrofuran (THF) (50ml) and triethylamine (7.1ml, 0.05mol), stir cooling down the dropping Benzoyl chloride (5.9ml, 0.05mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product white solid 8.4g, productive rate 89%, mp=84～85 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.24～8.25(13H，m，ArH)，2.92～3.00(2H，m，CH
2)，1.14～1.19(3H，t，CH
3)。
Embodiment 6 compounds 2 '-benzoyloxy methyl phenyl ketone synthetic
In the reaction flask of a 250ml, after nitrogen blows row, add the 2-acetyl phenol (3.2g, 0.025mol), tetrahydrofuran (THF) (50ml) and triethylamine (7.1ml, 0.05mol), stir cooling down the dropping Benzoyl chloride (5.9ml, 0.05mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product light yellow solid 5.2g, productive rate 87%, mp=78～80 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.23～8.23(9H，m，ArH)，2.55(3H，s，CH
3)。
Embodiment 7 compounds 2 '-benzoyloxy acetonaphthone synthetic
In the reaction flask of a 250ml, after nitrogen blows row, add 1-ethanoyl-beta naphthal (4.6g, 0.025mol), tetrahydrofuran (THF) (50ml) and triethylamine (7.1ml, 0.05mol), stir cooling down the dropping Benzoyl chloride (5.9ml, 0.05mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product white solid 6.2g, productive rate 86%, mp=80～82 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.38～8.23(11H，m，ArH)，2.63(3H，s，CH
3)。
Embodiment 8 compounds 2 '-benzoyloxy-4 '-benzoyloxy acetylamino phenyl propyl ketone synthetic
In the reaction flask of a 250ml, after nitrogen blows row, adding 2 '-hydroxyl-4 '-kharophen phenyl propyl ketone (4.4g, 0.02mol), tetrahydrofuran (THF) (50ml) and triethylamine (11.5ml, 0.04mol), dropping Benzoyl chloride under the stirring cooling (9.5ml, 0.04mol).Dropwise back room temperature reaction 1h, heating reflux reaction 6h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product white solid 7.0g, productive rate 82%, mp=109～111 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.51～8.19(13H，m，ArH)，2.77～2.82(2H，t，COCH
2)，2.02(3H，s，CH
3)，1.57～1.69(2H，m，CH
2)，0.84～0.89(3H，t，CH
3)。
Embodiment 9 compounds 1 '-benzoyloxy-2 '-acetonaphthone synthetic
In the reaction flask of a 250ml, after nitrogen blows row, add 2 acetyl naphthalene phenol (4.6g, 0.025mol), tetrahydrofuran (THF) (50ml) and triethylamine (7.1ml, 0.05mol), stir cooling down the dropping Benzoyl chloride (5.9ml, 0.05mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product white solid 6.3g, productive rate 88%, mp=118～120 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.51～8.37(11H，m，ArH)，2.64(3H，s，CH
3)。
Synthesizing of embodiment 10 compound 2-butyryl acyloxy benzophenone
In the reaction flask of a 250ml, after nitrogen blows row, add 2-benzoyl phenol (5.0g, 0.025mol), tetrahydrofuran (THF) (50ml) and triethylamine (7.1ml, 0.05mol), stir cooling down the dropping butyryl chloride (5.3ml, 0.05mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains the light yellow slightly slime body 5.5g of product, productive rate 82%.
1H-NMR(δ，ppm，TMS，CDCl
3)：6.93～7.78(9H，m，ArH)，2.13～2.18(2H，t，COCH
2)，1.46～1.54(2H，m，CH
2)，0.83～0.88(3H，t，CH
3)。
Synthesizing of the hot alkoxy benzophenone of embodiment 11 compound 2-benzoyloxys-4-
In the reaction flask of a 250ml, after nitrogen blows row, add the hot alkoxy benzophenone of 2-hydroxyl-4-(6.5g, 0.02mol), tetrahydrofuran (THF) (50ml) and triethylamine (5.8ml, 0.04mol), stir cooling down the dropping Benzoyl chloride (4.7ml, 0.04mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains the light yellow slightly cementation body of product 7.0g, productive rate 81%.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.31～8.17(11H，m，ArH)，6.85～6.89(2H，m，ArH-OCH
3)，4.02～4.06(2H，t，OCH
2)，1.77～1.86(2H，m，CH
2)，1.26～1.52(10H，m，CH
2)，0.87～0.91(3H，t，CH
3)。
Embodiment 12 compound 2-benzoyloxy-4-methoxyl groups-4 '-methyldiphenyl ketone synthetic
In the reaction flask of a 250ml, after nitrogen blows row, adding 2-hydroxyl-4-methoxyl group-4 '-methyldiphenyl ketone (7.3g, 0.03mol), tetrahydrofuran (THF) (50ml) and triethylamine (8.7ml, 0.06mol), dropping Benzoyl chloride under the stirring cooling (7.1ml, 0.06mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product white solid 7.2g, productive rate 69%, mp=88～90 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：6.86～8.12(12H，m，ArH)，3.88(3H，s，OCH
3)，2.30(3H，s，ArCH
3)。
Synthesizing of embodiment 13 compound 2-benzoyloxy-4-methoxy benzophenones
In the reaction flask of a 250ml, after nitrogen blows row, add 2-hydroxyl-4-methoxy benzophenone (6.8g, 0.03mol), tetrahydrofuran (THF) (50ml) and triethylamine (8.7ml, 0.06mol), stir cooling down the dropping Benzoyl chloride (7.1ml, 0.06mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product white solid 8.5g, productive rate 85%, mp=94～95 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：6.87～7.86(13H，m，ArH)，3.89(3H，s，OCH
3)。
Synthesizing of embodiment 14 compounds styryl-2-benzoyloxy benzophenone
In the reaction flask of a 250ml, after nitrogen blows row, add styryl-2-Viosorb 110 (4.5g, 0.02mol), tetrahydrofuran (THF) (50ml) and triethylamine (5.8ml, 0.04mol), stir cooling down the dropping Benzoyl chloride (4.7ml, 0.04mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains the light yellow needle-like solid 5.4g of product, productive rate 82%, mp=88～89 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.30～8.14(14H，m，ArH)，7.13(1H，s，CH＝CH)，7.18(1H，m，CH＝CH)。
Embodiment 15 compound 2-chloro-3 ', 4 '-dibenzoyl oxygen benzoylformaldoxime synthetic
In the reaction flask of a 250ml, after nitrogen blows row, adding 2-chloro-3 ', 4 '-resacetophenone (5.6g, 0.03mol), tetrahydrofuran (THF) (40ml) and triethylamine (17.4ml, 0.12mol), dropping Benzoyl chloride under the stirring cooling (14.4ml, 0.12mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains the light yellow sticky solid 8.6g of product, productive rate 73%.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.36～8.30(13H，m，ArH)，5.61(1H，s，COCH
2Cl)，4.71(1H，s，COCH
2Cl)。
Synthesizing of embodiment 16 compound 2-benzoyloxys-5-bromine benzophenone
In the reaction flask of a 250ml, after nitrogen blows row, add 2-hydroxyl-5-bromine benzophenone (5.0g, 0.018mol), tetrahydrofuran (THF) (40ml) and triethylamine (5.2ml, 0.036mol), stir cooling down the dropping Benzoyl chloride (4.3ml, 0.036mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product white solid 5.6g, productive rate 82%, mp=118～120 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.27～7.79(13H，m，ArH)。
Embodiment 17 compounds 2,4-dibenzoyl oxygen base benzophenone synthetic
In the reaction flask of a 250ml, after nitrogen blows row, add 2,4 dihydroxyl benzophenone (6.4g, 0.03mol), tetrahydrofuran (THF) (60ml) and triethylamine (17.4ml, 0.12mol), stir cooling down the dropping Benzoyl chloride (14.2ml, 0.12mol).Dropwise back room temperature reaction 1h, heating reflux reaction 6h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product white solid 9.5g, productive rate 75%, mp=135～136 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.29～8.23(18H，m，ArH)。
Embodiment 18 compounds 2,2 '-dibenzoyl oxygen base-4,4 '-dimethoxy-benzophenone synthetic
In the reaction flask of a 250ml, after nitrogen blows row, add 2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone (8.2g, 0.03mol), tetrahydrofuran (THF) (60ml) and triethylamine (17.47ml, 0.12mol), dropping Benzoyl chloride under the stirring cooling (14.2ml, 0.12mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product white solid 11.0g, productive rate 76%.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.36～7.90(12H，m，ArH)，6.65～6.68(4H，m，ArH-OCH
3)，3.72(6H，s，OCH
3)。
Embodiment 19 compounds 2 ', 5 '-dibenzoyl oxygen base Propiophenone synthetic
In the reaction flask of a 250ml, after nitrogen blows row, add 2 ', 5 '-dihydroxyphenyl-1-propanone (5.0g, 0.03mol), tetrahydrofuran (THF) (60ml) and triethylamine (17.47ml, 0.12mol), stir cooling down the dropping Benzoyl chloride (14.2ml, 0.12mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product light yellow solid 9.1g, productive rate 81%, mp=96～98 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.29～8.23(13H，m，ArH)，2.88～2.95(2H，m，COCH
2)，1.10～1.13(3H，t，CH
3)。
Embodiment 20 compounds 2 '-benzoyloxy-4 '-fluoro acetophenone synthetic
In the reaction flask of a 250ml, after nitrogen blows row, add 2 '-hydroxyl-4 '-fluoro acetophenone (5.0g, 0.032mol), tetrahydrofuran (THF) (50ml) and triethylamine (9.4ml, 0.064mol), stir cooling down the dropping Benzoyl chloride (7.7ml, 0.064mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains the colourless slightly slime body 7.2g of product, productive rate 87%.
1H-NMR(δ，ppm，TMS，CDCl
3)：6.97～8.21(8H，m，ArH)，2.52(3H，s，COCH
3)。
Embodiment 21 compounds 3 ', 5 '-two chloro-2 '-benzoyloxy methyl phenyl ketone synthetic
In the reaction flask of a 250ml, after nitrogen blows row, adding 3 ', 5 '-two chloro-2 '-hydroxy acetophenone (5.0g, 0.024mol), tetrahydrofuran (THF) (50ml) and triethylamine (7.2ml, 0.06mol), dropping Benzoyl chloride under the stirring cooling (5.7ml, 0.06mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product light yellow solid 7.2g, productive rate 87%, mp=96～97 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.48～8.24(7H，m，ArH)，2.52(3H，s，COCH
3)。
Embodiment 22 compounds 2,4,2 ', 4 '-four benzoyloxy benzophenone synthetic
In the reaction flask of a 250ml, after nitrogen blows row, add 2,4,2 ', 4 ' tetrahydroxybenzophenone (7.4g, 0.03mol), tetrahydrofuran (THF) (50ml) and pyridine (19.4ml, 0.24mol), stir cooling down the dropping Benzoyl chloride (28.4ml, 0.24mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product white solid 9.9g, productive rate 50%, mp=100～102 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.16～8.19(26H，m，ArH)。
Embodiment 23 compounds 2 ', 4 '-dibenzoyl oxygen benzoylformaldoxime synthetic
In the reaction flask of a 250ml, after nitrogen blows row, add 2 ', 4 '-resacetophenone (4.6g, 0.03mol), tetrahydrofuran (THF) (50ml) and triethylamine (17.4ml, 0.12mol), stir cooling down the dropping Benzoyl chloride (14.2ml, 0.12mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product light yellow solid 7.0g, productive rate 65%, mp=78～80 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.22～8.23(13H，m，ArH)，2.56(3H，s，COCH
3)。
Embodiment 24 compounds 3 ', 4 '-dibenzoyl oxygen benzoylformaldoxime synthetic
In the reaction flask of a 250ml, after nitrogen blows row, add 3 ', 5 '-resacetophenone (4.6g, 0.03mol), tetrahydrofuran (THF) (50ml) and triethylamine (17.4ml, 0.12mol), stir cooling down the dropping Benzoyl chloride (14.2ml, 0.12mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product light yellow solid 7.9g, productive rate 73%, mp=85～87 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.43～8.22(13H，m，ArH)，2.63(3H，s，COCH
3)。
Embodiment 25 compounds 3 ', 4 '-dibenzoyl oxygen base benzophenone synthetic
In the reaction flask of a 250ml, after nitrogen blows row, add 3 ', 4 '-dihydroxy benaophenonel (5.0g, 0.023mol), tetrahydrofuran (THF) (50ml) and triethylamine (14.4ml, 0.1mol), stir cooling down the dropping Benzoyl chloride (11.8ml, 0.1mol).Dropwise back room temperature reaction 1h, heating reflux reaction 5h, cool to room temperature.Add the saturated sodium-chloride water solution dissolved solids, ethyl acetate extraction 2 times.Merge organic phase, remove behind the anhydrous sodium sulfate drying and desolvate.Column chromatography, use sherwood oil: the mixture of ethyl acetate is made eluent, obtains product light yellow solid 6.9g, productive rate 71%, mp=82～84 ℃.
1H-NMR(δ，ppm，TMS，CDCl
3)：7.36～8.08(18H，m，ArH)。
Two, the preparation of embodiment 1～25 and comparative example 1 ingredient of solid catalyst
Above-mentioned synthetic compound is prepared olefins polymerizing solid catalyst component as follows 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 keeps 2.5h, solid dissolves fully, adds Tetra hydro Phthalic anhydride 1.4g, continues to keep 1h.Solution is cooled to below-25 ℃, drips TiCl in the 1h
456ml slowly is warming up to 80 ℃, separates out solids in temperature-rise period gradually, adds preparation the foregoing description 1～18 synthetic compound 6mmol respectively, and holding temperature 1h after the filtration, with toluene 70ml washing secondary, obtains solid sediment respectively.Add toluene 60ml then, TiCl
440ml is warmed up to 110 ℃, keeps 2h, and same operation repeats once, washs three times down at 110 ℃ with toluene 70ml again, and the time respectively is 10min, adds hexane 60ml again, washed twice.Obtain ingredient of solid catalyst.
Comparative example 1:
Press the preparation method of the ingredient of solid catalyst of the foregoing description, just internal electron donor is replaced with n-butyl phthalate (DNBP).
Three, 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 catalyst component 10mg and the 1.2L hydrogen of embodiment 1～21 and Comparative Examples 1 again, feeds liquid propene 2.5L, be warming up to 70 ℃, keep this temperature 1h, pressure is put in cooling, discharging gets the PP resin, calculate its activity, measure the isotactic index of resulting polymers, concrete outcome sees Table 1.
The catalyst component propylene polymerization condition of embodiment 1,5 and Comparative Examples 1 is constant, changes the add-on of hydrogen when being polymerization, and concrete outcome sees Table 2
Table 1
By the data of table 1 as can be seen, when catalyst component of the present invention is used for propylene polymerization, can obtain gratifying polymerization activity, and the stereospecificity of polymkeric substance is higher.
Table 2
From the data of table 2 embodiment and Comparative Examples more as can be seen, when adopting catalyst component of the present invention to be used for propylene polymerization, not only the degree of isotacticity of catalyst activity, polymkeric substance still keeps very high level, catalyzer has extraordinary hydrogen response, the molecular weight distribution broad of resulting polymers simultaneously.
Claims (16)
1. the catalyst component that is used for olefinic polymerization, it comprises magnesium, titanium, halogen and electron donor compound, and this electron donor compound is selected from least a in following general formula (I) compound:
R wherein
1, R
2Can be identical or inequality, be C
1～C
10Alkyl or cycloalkyl, the C of straight or branched
5～C
20Aryl or aralkyl; R
3, R
4, R
5Can be identical or inequality, be C
1～C
10The alkyl of straight or branched or alkoxyl group, C
5～C
15Aryl or aralkyl, hydrogen, halogen, acyl group, ester group, amide group or amino.
2. the catalyst component that is used for olefinic polyreaction according to claim 1, in the compound of wherein said general formula (I), R
1, R
2Be C
1～C
6Alkyl or cycloalkyl, the C of straight or branched
5～C
20Aryl or aralkyl.
3. the catalyst component that is used for olefinic polyreaction according to claim 2, in the compound of wherein said general formula (I), R
1, R
2Be C
5～C
20Aryl.
4. the catalyst component that is used for olefinic polyreaction according to claim 3, in the compound of wherein said general formula (I), R
1, R
2Be phenyl.
5. the catalyst component that is used for olefinic polyreaction according to claim 1, in the compound of wherein said general formula (I), R
3, R
4, R
5Be C
1～C
8The alkyl of straight or branched or alkoxyl group, C
5～C
15Aryl or aralkyl, hydrogen, halogen, acyl group, ester group or amide group.
6. the catalyst component that is used for olefinic polyreaction according to claim 5, in the compound of wherein said general formula (I), R
3, R
4, R
5Be hydrogen, halogen or ester group.
7. the catalyst component that is used for olefinic polyreaction according to claim 1, in the compound of wherein said general formula (I), phenyl ring can be replaced by naphthalene nucleus or other condensed ring.
8. according to the described catalyst component that is used for olefinic polymerization of one of claim 1～7, it comprises titanium compound, magnesium compound and is selected from the reaction product of the compound of general formula (I);
Wherein said 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.
9. the catalyst component that is used for olefinic polyreaction according to claim 8, described each component are in every mole of magnesium compound, and titanium compound is 0.5～150 mole, and the compound of general formula (I) is 0.02～0.4 mole.
10. the catalyst component that is used for olefinic polymerization according to claim 8, the magnesium compound that it adopted is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds.
11. the catalyst component that is used for olefinic polymerization according to claim 8, the magnesium compound that it adopted is the alcohol adduct of magnesium dihalide.
12. 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 1～11;
(2) alkylaluminium cpd;
(3) randomly, external electron donor component.
13. catalyzer according to claim 12, wherein the external electron donor component is selected from general formula R
nSi (OR ')
4-nCompound, 0≤n in the formula≤3, R is of the same race or different alkyl, cycloalkyl, aryl, haloalkyl, amino with R ', R randomly is halogen or hydrogen atom.
14. one kind is used for alkene CH
2=CHR polymeric pre-polymerized catalyst, wherein R is hydrogen or C
1～C
12Alkyl group, described pre-polymerized catalyst comprises a kind of according to each described ingredient of solid catalyst or catalyzer in the claim 1～11, carry out the prepolymer of prepolymerization gained with alkene, the pre-polymerization multiple is 0.1～1000g olefin polymer/g ingredient of solid catalyst.
15. pre-polymerized catalyst according to claim 14, wherein carrying out prepolymerized alkene is ethene or propylene.
16. be used for alkene CH
2=CHR polymeric method, wherein R is the hydrocarbyl group of hydrogen or 1～12 carbon atom, carries out in the presence of each described catalyzer or the pre-polymerized catalyst in claim 12～15.
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Cited By (6)
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| CN103665200A (en) * | 2012-09-06 | 2014-03-26 | 中国石油化工股份有限公司 | Solid catalyst component used for olefin polymerization, catalyst and application |
| CN104350073A (en) * | 2012-05-23 | 2015-02-11 | 巴塞尔聚烯烃意大利有限公司 | Catalyst components for the polymerization of olefins |
| CN104558302A (en) * | 2013-10-29 | 2015-04-29 | 中国石油天然气股份有限公司 | Propylene polymerization catalyst |
| CN110283080A (en) * | 2019-07-05 | 2019-09-27 | 山西大学 | A kind of fluorine-containing benzophenone derivates and its preparation method and application |
| CN112125793A (en) * | 2020-09-16 | 2020-12-25 | 宜都市华阳化工有限责任公司 | 2, 4-di-n-octyloxy benzophenone and synthesis method and application thereof |
| CN113880977A (en) * | 2021-10-18 | 2022-01-04 | 万华化学集团股份有限公司 | Olefin polymerization catalyst, preparation method and application |
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| CN104350073A (en) * | 2012-05-23 | 2015-02-11 | 巴塞尔聚烯烃意大利有限公司 | Catalyst components for the polymerization of olefins |
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| CN110283080A (en) * | 2019-07-05 | 2019-09-27 | 山西大学 | A kind of fluorine-containing benzophenone derivates and its preparation method and application |
| CN112125793A (en) * | 2020-09-16 | 2020-12-25 | 宜都市华阳化工有限责任公司 | 2, 4-di-n-octyloxy benzophenone and synthesis method and application thereof |
| CN113880977A (en) * | 2021-10-18 | 2022-01-04 | 万华化学集团股份有限公司 | Olefin polymerization catalyst, preparation method and application |
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