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CN107417813A - A kind of ingredient of solid catalyst and catalyst for olefinic polymerization - Google Patents

A kind of ingredient of solid catalyst and catalyst for olefinic polymerization Download PDF

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Publication number
CN107417813A
CN107417813A CN201610344188.0A CN201610344188A CN107417813A CN 107417813 A CN107417813 A CN 107417813A CN 201610344188 A CN201610344188 A CN 201610344188A CN 107417813 A CN107417813 A CN 107417813A
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compound
group
citric acid
catalyst
alkyl
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Inventor
王志武
李树行
李华姝
张军伟
代金松
马庆利
胡乐
陈灏
王星火
焦文杰
高勇
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Beijing Li Hezhixin Science And Technology Ltd
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Beijing Li Hezhixin Science And Technology Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • C08F4/6543—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium
    • C08F4/6545—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium and metals of C08F4/64 or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
    • C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/651—Pretreating with non-metals or metal-free compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • C08F4/6548—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof magnesium or compounds thereof, not provided for in C08F4/6543 or C08F4/6546

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Emergency Medicine (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention discloses a kind of ingredient of solid catalyst for olefinic polymerization, and it contains Mg, Ti, halogen and internal electron donor, wherein, the internal electron donor is selected from as led at least one of citric acid ester compound shown in formula (I).The invention also discloses the application containing the catalyst of the ingredient of solid catalyst and the catalyst in olefinic polyreaction, the application particularly in propylene polymerization.The present invention is applied to citric acid ester type compound as electron donor in the preparation for olefin polymerization catalysis, obtained catalyst has the characteristics of hydrogen tonality is good, polyolefin suitable for preparing wide molecular weight distribution, the exploitation of be particularly suitable for use in foodstuffs without toxicity and the high-end trade mark polyolefin products of medical treatment.

Description

A kind of ingredient of solid catalyst and catalyst for olefinic polymerization
Technical field
The present invention relates to one kind to be used for CH2The catalytic component of=CHR olefinic polymerizations, wherein, R is for hydrogen or containing 1-12 The hydrocarbyl group of individual carbon atom.A kind of more particularly it relates to solid containing at least one citric acid ester compound Catalytic component.Moreover, it relates to it is a kind of containing the catalyst of the ingredient of solid catalyst and the catalyst in alkene Application in polymerized hydrocarbon reaction, the application especially in propylene polymerization.
Background technology
In propylene polymerization industry, the catalyst studied and be most widely used is Ziegler-Natta (Z-N) catalyst, should Catalyst be during carrying out load titanium to active magnesium chloride support add internal electron donor prepared by.Due to interior to electricity Daughter can farthest change catalyst performance, and therefore, studying and find preferable internal electron donor compound turns into Z-N The focus and focus of catalyst research.
At present, industrial quarters is generally using binary aromatic carboxylic acid's ester type compound as internal electron donor, although catalyst activity Use, but the relative molecular mass distribution liquid of the polypropylene (PP) as made from the catalyst is narrower, and phthalic acid Ester type compound has very big harm to the healthy reproduction and environment of people.With the passage of usage time, phthalic acid ester Class compound can be transferred in environment by plastics, cause the pollution to water body etc..In the lake in China, rivers and well water Phthalate compound, most commonly n-butyl phthalate (DNBP) and neighbour are all generally detected Phthalic acid two (2 ,-ethylhexyl) ester (DEHP).Because human body is with the contact of plastic products, in plastic products Phthalate compound can also pass through human body, in turn result in harm.Although the acute poison of phthalate Property intensity is little, but in the case of heavy dose, it has monster and mutagenic consequence to animal.Due to olefinic polymerization Catalyst, as internal electron donor, is remained mostly using such compound so also having very small amount in Product olefins resin. Although concentration of the phthalate compound from catalyst in resin is only 2~5ppm, on being normally applied It meets safety standard, and still, in some special dimensions, especially medical field, its application may also suffer from Limitation.For example, the DEHP for having 50-70ppm is entered after 4 DEG C preserve one day with the blood plasma that PVC bag is stored Blood plasma, patient will cause expiratory dyspnea, lung originality shock etc. after inputting this blood plasma, and severe patient even results in death.
Using catalyst of the non-phthalic acid ester class compound as internal electron donor, it is referred to as " non-neighboring " catalyst.This The research of class catalyst turns to improvement product combination property from raising catalyst efficiency is focused on, and improved main target is to improve To the control ability of polymer performance；On the other hand, by reducing or preventing use as far as possible to human body health and nature Environment reduces and eliminated industrial production from source to health and environment by industrial chemicals such as the phthalates that endangers Pollution, and keep or obtain more excellent catalytic performance simultaneously, turn into a big focus of this area research and development.At present, Representational non-neighboring catalyst has：Dutch LyondellBasell companies diether catalyst (for example, EP03611493, ) and succinate catalyst (for example, WO9856834, WO0063261, WO03022894) EP0728724.With 1,3- diether be the catalyst of internal electron donor compared with phthalic acid ester is the catalyst series of electron donor, its activity Further improve, the relative molecular mass distribution of obtained polymer is narrower, and hydrogen regulation performance is good, it is not necessary to external electron donor It can obtain high isotatic polypropylene.But isotacticity then needs silane to be used as outer to electricity as that need to reach higher level Daughter.The catalyst series can be used for production high fluidity, the polypropylene product of narrow molecular weight distribution.And amber Compared with phthalic acid ester is the catalyst series of electron donor, its activity increases acid esters internal electron donor catalyst, The relative molecular mass distribution of resulting polymer is wider, and the rigidity and processing characteristics of the acrylic resin of production obtain Improve, low melt flow speed (MFR) heterophasic copolymer of production has preferable rigidity and impact strength.The series Catalyst is applied to most of PP Production Technology, including substance law, vapor phase method, slurry process and most of body-gas phase Method group technology.Developed by Sinopec Beijing Chemical Research Institute 1,3- diol-lipids catalyst (for example, WO9856834, WO0063261, WO03022894) fall within it is such.It is reported that its performance can reach diether and succinate compound is urged Agent peer-level is with China's independent intellectual property right and is applied to industrial latest generation catalyst.
However, in actual applications, above-claimed cpd still has one as the internal electron donor of catalyst for olefines polymerizing Determine problem, for example, using catalyst of 1, the 3- diether compounds as internal electron donor, although its activity is higher, and Catalyst hydrogen response, but obtained polyacrylic relative molecular mass distribution is narrow, is unfavorable for developing different boards Number PP；And succinate compound compound is used as internal electron donor, its advantage is the PP relative molecular masses of synthesis Wider distribution, but PP stereoregularity and the hydrogen response of catalyst are to be improved；And diol-lipid catalytic body The activity of system is overall be not as preferable as two ethers systems.Although what is more important, above-claimed cpd belong to " non-neighboring " chemical combination Thing, but be not mostly innocuous substance by definitely certification, therefore its contamination to environment can not be excluded, and this Limit the application in its production in some high-end non-toxic materials.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide one kind to be applied to CH2=CHR olefinic polymerizations are consolidated Body catalyst component, wherein, R is hydrogen or the hydrocarbyl group containing 1-12 carbon atom.
Another object of the present invention is to provide a kind of preparation method of ingredient of solid catalyst as described above.
It is still another object of the present invention to provide a kind of catalyst containing ingredient of solid catalyst as described above.
To achieve the above object, the present invention uses following technical scheme：
It is of the present invention to be used for CH2The ingredient of solid catalyst of=CHR olefinic polymerizations, wherein, R is for hydrogen or containing 1-12 The hydrocarbyl group of individual carbon atom, it includes Mg, Ti, halogen and electron donor, wherein, the electron donor is selected from as logical At least one citric acid ester compound shown in formula (I)：
Wherein, in logical formula (I) as implied above, R1、R2And R3Group is C that is identical or differing1-C20Alkyl, For example, C1-C20Straight or branched alkyl, alkenyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl and C7-C20Aryl；Preferably, R1、R2And R3Cyclization can be bonded mutually；R is hydrogen, or is C1-C20Alkyl, Or it is C2-C21Acyl group.In addition, the R1-R3With in R can also arbitrarily comprising one or several halogen atoms or N, the hetero atom such as O, S, P, Si, Ge.
In logical formula (I) as implied above, R1、R2And R3Group be preferably selected from methyl, ethyl, propyl group, isopropyl, Butyl, the tert-butyl group, isobutyl group, amyl group, cyclopenta, neopentyl, hexyl, cyclohexyl, heptyl, octyl group, nonyl, Decyl, undecyl~eicosyl, the alkenyl less than 20 carbon, ester group, phenyl, alkyl phenyl, phenylalkyl, Indenyl, benzyl, halo or the cycloalkyl substituted by hetero atoms such as N, O, S, P, Si, Ge, phenyl, alkyl phenyl, Phenylalkyl, indenyl, benzyl；Or selected from heterocyclic aryl substituent, as furans, thiophene, pyrroles, thiazole, imidazoles, Pyridine, pyrazine, pyrimidine, pyridazine, indoles, quinoline, pteridine, acridine；R1、R2And R3Group can be with identical or not Together；And R1、R2And R3Cyclization can be bonded mutually.
In logical formula (I) as implied above, R is hydrogen either C1-C20Alkyl；When R is C1-C20Alkyl when, It is preferably C1-C20Straight or branched alkyl, alkenyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl And C7-C20Aryl；Further, when R is C1-C20Alkyl when, its be preferably selected from methyl, ethyl, propyl group, Isopropyl, butyl, the tert-butyl group, isobutyl group, amyl group, cyclopenta, neopentyl, hexyl, cyclohexyl, heptyl, octyl group, Nonyl, decyl, undecyl~eicosyl, the alkenyl less than 20 carbon, ester group, phenyl, alkyl phenyl, phenyl Alkyl, indenyl, benzyl, halo or the cycloalkyl substituted by hetero atoms such as N, O, S, P, Si, Ge, phenyl, alkane Base phenyl, phenylalkyl, indenyl, benzyl；Or selected from heterocyclic aryl substituent for example furans, thiophene, pyrroles, thiazole, Imidazoles, pyridine, pyrazine, pyrimidine, pyridazine, indoles, quinoline, pteridine, acridine.
Preferably, in logical formula (I) as implied above, when R is C2-C21Acyl group when, it, which has, is selected from such as logical formula (II) Shown acyl group citric acid ester compound structure：
Wherein, in logical formula (II) as implied above, the R4Group is C1-C20Alkyl, for example, C1-C20Straight chain Or branched alkyl, alkenyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl and C7-C20Aryl, enter One step, the R4Group is preferably selected from methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group, isobutyl group, penta Base, cyclopenta, neopentyl, hexyl, cyclohexyl, heptyl, octyl group, nonyl, decyl, undecyl~eicosyl, Less than the alkenyl of 20 carbon, ester group, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl, halo or by N, O, S, the cycloalkyl of the hetero atom such as P, Si, Ge substitution, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl；Or Selected from heterocyclic aryl substituent such as furans, thiophene, pyrroles, thiazole, imidazoles, pyridine, pyrazine, pyrimidine, pyridazine, Yin Diindyl, quinoline, pteridine, acridine.
Specifically, the citric acid ester compound in the present invention logical formula (I) as implied above includes but is not limited to：
Citric acid ester type compound：Trimethyl citrate, triethyl citrate, the propyl ester of citric acid three, the isopropyl of citric acid three Ester, ATBC, the tert-butyl ester of citric acid three, tri-iso-butyl citrate, tripentyl citrates, the ring penta of citric acid three Ester, the peopentyl ester of citric acid three, THC, the cyclohexyl of citric acid three, the heptyl ester of citric acid three, trioctyl lemon acid, The nonyl ester of citric acid three, citric acid three last of the ten Heavenly stems ester, citric acid three (hendecane base ester)~hydroxycitric acid three (eicosane base ester)；
Ether citric acid ester type compound：Methyl ether trimethyl citrate, methyl ether triethyl citrate, methyl ether lemon Sour three propyl ester, the isopropyl ester of methyl ether citric acid three, methyl ether ATBC, the tert-butyl ester of methyl ether citric acid three, first Base ether tri-iso-butyl citrate, methyl ether tripentyl citrates, the ring pentyl ester of methyl ether citric acid three, methyl ether citric acid three Peopentyl ester, methyl ether THC, the cyclohexyl of methyl ether citric acid three, the heptyl ester of methyl ether citric acid three, methyl ether Trioctyl lemon acid, the nonyl ester of methyl ether citric acid three, methyl ether citric acid three last of the ten Heavenly stems ester, (hendecane of methyl ether citric acid three Base ester)~methyl ether citric acid three (eicosane base ester)；Ethylether trimethyl citrate, ethylether triethyl citrate, The propyl ester of ethylether citric acid three, the isopropyl ester of ethylether citric acid three, ethylether ATBC, ethylether citric acid three The tert-butyl ester, ethylether tri-iso-butyl citrate, ethylether tripentyl citrates, the ring pentyl ester of ethylether citric acid three, ethyl The peopentyl ester of ether citric acid three, ethylether THC, the cyclohexyl of ethylether citric acid three, ethylether citric acid three heptan Ester, ethylether trioctyl lemon acid, the nonyl ester of ethylether citric acid three, ethylether citric acid three last of the ten Heavenly stems ester, ethylether citric acid Three (hendecane base ester)~ethylether citric acids three (eicosane base ester)；Propyl ether trimethyl citrate~propyl ether lemon Sour three (eicosane base esters)；Butyl ether trimethyl citrate~butyl ether citric acid three (eicosane base ester)；
Acyl group citric acid ester type compound：Acetyl citrate trimethyl, CitroflexA-2, acetyl group lemon Sour three propyl ester, the isopropyl ester of acetyl citrate three, citroflex A-4, the tert-butyl ester of acetyl citrate three, second Acyl group tri-iso-butyl citrate, acetyl citrate triamyl, the ring pentyl ester of acetyl citrate three, acetyl citrate three Peopentyl ester, three own ester of acetyl citrate, the cyclohexyl of acetyl citrate three, the heptyl ester of acetyl citrate three, acetyl group Trioctyl lemon acid, the nonyl ester of acetyl citrate three, acetyl citrate three last of the ten Heavenly stems ester, (hendecane of acetyl citrate three Base ester)~acetyl citrate three (eicosane base ester)；(just, different) propiono trimethyl citrate~(just, different) third Acyl group citric acid three (eicosane base ester)；(just, different, uncle) bytyry trimethyl citrate~(just, different, uncle) fourth Acyl group citric acid three (eicosane base ester)；(just, different, new) valeryl trimethyl citrate~(just, different, new) penta Acyl group citric acid three (eicosane base ester)；The formoxyl trimethyl citrate of the ring penta~(eicosane of penta formoxyl citric acid of ring three Base ester)；Caproyl trimethyl citrate~caproyl citric acid three (eicosane base ester)；Hexamethylene formoxyl citric acid front three Ester~hexamethylene formoxyl citric acid three (eicosane base ester)；Heptanoyl group trimethyl citrate~heptanoyl group citric acid three (20 Arrcostab)；Caprylyl trimethyl citrate~caprylyl citric acid three (eicosane base ester)；Pelargonyl group trimethyl citrate~ Pelargonyl group citric acid three (eicosane base ester)；Capryl trimethyl citrate~capryl citric acid three (eicosane base ester)； Lauroyl trimethyl citrate~lauroyl citric acid three (eicosane base ester)；Myristoyl trimethyl citrate~ Myristoyl citric acid three (eicosane base ester)；Palmityl trimethyl citrate~palmityl citric acid three (20 Arrcostab)；Pearly-lustre acyl group trimethyl citrate~pearly-lustre acyl group citric acid three (eicosane base ester)；Stearyl citric acid Trimethyl~stearyl citric acid three (eicosane base ester)；Peanut acyl group trimethyl citrate~peanut acyl group citric acid three (eicosane base ester)；Benzoyl trimethyl citrate~benzoyl citric acid three (eicosane base ester)；Phenylacetyl group Trimethyl citrate~phenylacetyl group citric acid three (eicosane base ester)；To chlorobenzene formacyl trimethyl citrate~to chlorobenzene Formoxyl citric acid three (eicosane base ester)；Adjacent chlorobenzene formacyl trimethyl citrate~adjacent chlorobenzene formacyl citric acid three (two Ten Arrcostabs)；Between chlorobenzene formacyl trimethyl citrate~chlorobenzene formacyl citric acid three (eicosane base ester)；To first Epoxide benzoyl trimethyl citrate~to methoxybenzoyl base citric acid three (eicosane base ester)；Between fluorobenzoyl lemon A lemon acid trimethyl~fluoro benzoyl citric acid three (eicosane base ester)；To fluorobenzoyl trimethyl citrate~to fluorobenzene Formoxyl citric acid three (eicosane base ester)；Adjacent fluorobenzoyl trimethyl citrate~adjacent fluoro benzoyl citric acid three (two Ten Arrcostabs)；To toluyl trimethyl citrate~to methyl benzoyl citric acid three (eicosane base ester)；It is right Nitrobenzene formyl trimethyl citrate~p-nitrophenyl formoxyl citric acid three (eicosane base ester)；Ethoxy oxalyl citric acid three Methyl esters~ethoxy oxalyl group citric acid three (eicosane base ester)；Furoyl trimethyl citrate~furanylcarbonyl citric acid Three (eicosane base esters)；Morpholine formyl trimethyl citrate~morpholine methanoyl citric acid three (eicosane base ester)；Thiophene Formyl trimethyl citrate~Thenoyl citric acid three (eicosane base ester)；Pyridinecarboxylic trimethyl citrate~pyridine Formoxyl citric acid three (eicosane base ester)；The propylene ether trimethyl citrate~(eicosyl of propylene ether citric acid three Ester)；Acryloyl group trimethyl citrate~acryloyl group citric acid three (eicosane base ester).
Specifically, acyl group citric acid ester compound in the present invention logical formula (II) as implied above, it includes but is not limited to： Triethyl citrate, ATBC, methyl ether trimethyl citrate, methyl ether triethyl citrate, methyl ether lemon Lemon acid three propyl ester, the isopropyl ester of methyl ether citric acid three, methyl ether ATBC, the tert-butyl ester of methyl ether citric acid three, Methyl ether tri-iso-butyl citrate, methyl ether tripentyl citrates, the ring pentyl ester of methyl ether citric acid three, methyl ether citric acid Three peopentyl esters, methyl ether THC, the cyclohexyl of methyl ether citric acid three, the heptyl ester of methyl ether citric acid three, methyl Ether trioctyl lemon acid, the nonyl ester of methyl ether citric acid three, methyl ether citric acid three last of the ten Heavenly stems ester, methyl ether citric acid three (11 Arrcostab)~methyl ether citric acid three (eicosane base ester)；
Acetyl citrate trimethyl, CitroflexA-2, the propyl ester of acetyl citrate three, acetyl citrate Three isopropyl esters, citroflex A-4, the tert-butyl ester of acetyl citrate three, the isobutyl ester of acetyl citrate three, second Acyl group tripentyl citrates, the ring pentyl ester of acetyl citrate three, the peopentyl ester of acetyl citrate three, acetyl citrate three Own ester, the cyclohexyl of acetyl citrate three, the heptyl ester of acetyl citrate three, the monooctyl ester of acetyl citrate three, acetyl group lemon Three nonyl esters of lemon acid, acetyl citrate three last of the ten Heavenly stems ester, acetyl citrate three (hendecane base ester)~acetyl citrate three (eicosane base ester)；(just, different) the propiono trimethyl citrate~(eicosane of (just, different) propiono citric acid three Base ester)；(just, different, uncle) the bytyry trimethyl citrate~(eicosane of (just, different, uncle) bytyry citric acid three Base ester)；(just, different, new) the valeryl trimethyl citrate~(eicosane of (just, different, new) valeryl citric acid three Base ester)；The formoxyl citric acid three (eicosane base ester) of the formoxyl trimethyl citrate of ring penta~ring penta；Caproyl citric acid Trimethyl~caproyl citric acid three (eicosane base ester)；Hexamethylene formoxyl trimethyl citrate~hexamethylene formoxyl citric acid Three (eicosane base esters)；Heptanoyl group trimethyl citrate~heptanoyl group citric acid three (eicosane base ester)；Caprylyl lemon Sour trimethyl~caprylyl citric acid three (eicosane base ester)；Pelargonyl group trimethyl citrate~pelargonyl group citric acid three (two Ten Arrcostabs)；Capryl trimethyl citrate~capryl citric acid three (eicosane base ester)；Lauroyl citric acid three Methyl esters~lauroyl citric acid three (eicosane base ester)；Myristoyl trimethyl citrate~myristoyl citric acid Three (eicosane base esters)；Palmityl trimethyl citrate~palmityl citric acid three (eicosane base ester)；Pearly-lustre acyl Base trimethyl citrate~pearly-lustre acyl group citric acid three (eicosane base ester)；Stearyl trimethyl citrate~stearyl Citric acid three (eicosane base ester)；Peanut acyl group trimethyl citrate~peanut acyl group citric acid three (eicosane base ester)； Benzoyl trimethyl citrate~benzoyl citric acid three (eicosane base ester)；Phenylacetyl group trimethyl citrate~benzene Acetyl citrate three (eicosane base ester)；To chlorobenzene formacyl trimethyl citrate~to chlorobenzene formacyl citric acid three (two Ten Arrcostabs)；Adjacent chlorobenzene formacyl trimethyl citrate~adjacent chlorobenzene formacyl citric acid three (eicosane base ester)；M-chloro A benzoyl trimethyl citrate~chlorobenzene formacyl citric acid three (eicosane base ester)；To methoxybenzoyl base lemon Sour trimethyl~to methoxybenzoyl base citric acid three (eicosane base ester)；Between a fluorobenzoyl trimethyl citrate~fluorine Benzoyl citric acid three (eicosane base ester)；To fluorobenzoyl trimethyl citrate~to fluoro benzoyl citric acid three (two Ten Arrcostabs)；Adjacent fluorobenzoyl trimethyl citrate~adjacent fluoro benzoyl citric acid three (eicosane base ester)；To methyl Benzoyl trimethyl citrate~to methyl benzoyl citric acid three (eicosane base ester)；P-nitrophenyl formyl citric acid three Methyl esters~p-nitrophenyl formoxyl citric acid three (eicosane base ester)；Ethoxy oxalyl trimethyl citrate~ethoxy oxalyl group lemon Lemon acid three (eicosane base ester)；Furoyl trimethyl citrate~furanylcarbonyl citric acid three (eicosane base ester)； Morpholine formyl trimethyl citrate~morpholine methanoyl citric acid three (eicosane base ester)；Thenoyl trimethyl citrate~ Thenoyl citric acid three (eicosane base ester)；Pyridinecarboxylic trimethyl citrate~pyridinecarboxylic acyl group citric acid three (two Ten Arrcostabs).
Further, in the present invention, the acyl group citric acid ester compound as shown in logical formula (II) is preferred：
Acetyl citrate trimethyl, CitroflexA-2, the propyl ester of acetyl citrate three, acetyl citrate Three isopropyl esters, citroflex A-4, the tert-butyl ester of acetyl citrate three, the isobutyl ester of acetyl citrate three, second Acyl group tripentyl citrates, the ring pentyl ester of acetyl citrate three, the peopentyl ester of acetyl citrate three, acetyl citrate three Own ester, the cyclohexyl of acetyl citrate three, the peanut ester of three heptyl esters of acetyl citrate~acetyl citrate three, (just, different) Propiono triethyl citrate；(just, different, uncle) bytyry triethyl citrate；(just, different, new) valeryl lemon Triethylenetetraminehexaacetic acid ester；The formoxyl triethyl citrate of ring penta；Caproyl triethyl citrate；Hexamethylene formoxyl triethyl citrate； Heptanoyl group triethyl citrate；Caprylyl triethyl citrate；Pelargonyl group triethyl citrate；Capryl lemon triethylenetetraminehexaacetic acid Ester；Lauroyl triethyl citrate；Myristoyl triethyl citrate；Palmityl triethyl citrate；Pearly-lustre Acyl triethyl citrate；Stearyl triethyl citrate；Peanut acyl triethyl citrate；Benzoyl citric acid Triethyl；Phenylacetyl group triethyl citrate；To chlorobenzene formacyl triethyl citrate；Adjacent chlorobenzene formacyl citric acid three Ethyl ester；Between chlorobenzene formacyl triethyl citrate；To methoxybenzoyl base triethyl citrate；Between fluorobenzoyl lemon Triethylenetetraminehexaacetic acid ester；To fluorobenzoyl triethyl citrate；Adjacent fluorobenzoyl triethyl citrate；To toluyl citric acid Triethyl；P-nitrophenyl formyl triethyl citrate；(just, different) propiono ATBC；(just, different, uncle) Bytyry ATBC；(just, different, new) valeryl ATBC；The formoxyl ATBC of ring penta； Caproyl ATBC；Hexamethylene formoxyl ATBC；Heptanoyl group ATBC；Caprylyl citric acid Tributyl；Pelargonyl group ATBC；Capryl ATBC；Lauroyl ATBC；Nutmeg Acyl group ATBC；Palmityl ATBC；Pearly-lustre acyl group ATBC；Stearyl citric acid Tributyl；Peanut acyl group ATBC；Benzoyl ATBC；Phenylacetyl group ATBC；It is right Chlorobenzene formacyl ATBC；Adjacent chlorobenzene formacyl ATBC；Between chlorobenzene formacyl ATBC； To methoxybenzoyl base ATBC；Between fluorobenzoyl ATBC；To fluorobenzoyl ATBC； Adjacent fluorobenzoyl ATBC；To toluyl ATBC；P-nitrophenyl formyl ATBC； Methoxyl group triethyl citrate；Methoxyl group ATBC.
Catalytic component of the present invention for olefinic polymerization, its may also include titanium compound, magnesium compound and it is interior to The reaction product of electron, wherein, the internal electron donor is as led in the citric acid ester compound shown in formula (I) extremely Few one kind；Further, in the present invention, the internal electron donor is as led to the acyl group citrate shown in formula (II) Chemical combination and the mixture as led to citric acid ester compound shown in formula (I), in addition to acyl group citric acid ester compound； The precursor of the magnesium compound is selected from XnMg(OR)2-n, MgCl2MROH, R2-nMgXn, MgCl2/SiO2, MgCl2/Al2O3Or at least one of mixture of magnesium halide and alcohol titanium, wherein, m be 0.1-6 number, 0≤n≤2, X is halogen, and R is hydrogen or C1-C20Alkyl；The formula of the titanium compound is TiXN(OR)4-N, wherein, R is carbon Atomicity is 1-20 alkyl, and X is halogen, N=0-4.
In the present invention, the magnesium compound preferably uses magnesium hydrocarbyloxy compound.Or the magnesium compound is preferable Using the alcohol adduct of magnesium dihalide.Again or, the preferable liquid magnesium compound of magnesium compound.
In the present invention, the titanium compound includes but is not limited to：Titanium tetrachloride, titanium tetrabromide, titanium tetra iodide or alkyl Halogenated titanium, wherein, the alkyl halide titanium, which can use, to be included but is not limited to：Methoxytitanium trichloride, ethyoxyl tri-chlorination Titanium, propoxyl group titanium trichloride, nbutoxytitanium trichloride, dimethoxy titanium chloride, diethoxy titanium chloride, two Propoxyl group titanium chloride, two n-butoxy titanium chloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy One or more in titanium chloride or three n-Butoxyl titanium-chlorides.In the present invention, the titanium compound preferably uses tetrachloro Change titanium.
Another object of the present invention, a kind of preparation of ingredient of solid catalyst as described above, it can pass through following several sides Method is carried out：
According to an embodiment of the present invention, the preparation method of the ingredient of solid catalyst, its step may include：With TiCl4Or aromatic hydrocarbons (such as toluene, dimethylbenzene etc.) solution of titanium alkoxides at -25-0 DEG C with such as dialkoxy magnesium or The two magnesium hydrocarbyloxy compounds reaction of two aryloxy group magnesium etc, and carry out halogenation at 80-130 DEG C.Use TiCl4Aromatic hydrocarbons it is molten The processing that liquid is carried out can be repeated one or more times, and the citric acid shown in logical formula (I) is added in repeatedly such processing Ester compounds.Such as it can refer to the preparation method system of the solids containing titanium catalytic component disclosed in US5077357 It is standby：Magnesium ethylate, purity titanium tetraethoxide, orthoresol, ethanol and chlorobenzene are sequentially added, is stirred；By TiCl4/ chlorobenzene solution Rapidly join in aforesaid liquid, heating until completely dissolved, is continuously heating to specified temp；Utilize N2Bubbling takes away ethanol Continue to stir certain time after reactant, then washed once using hot chlorobenzene, isooctane washes twice, then N2Drying can Obtain carrier.Or according to another example：Successively by TiCl4, purity titanium tetraethoxide, magnesium ethylate and orthoresol add in chlorobenzene, Stirring；Ethanol is added, continues to stir 3h after magnesium ethylate dissolving under high temperature；While hot then filtering is washed using warm chlorobenzene Once, isooctane washed once, last N2Dry.
According to another embodiment of the present invention, the preparation method of the ingredient of solid catalyst, its step may include：Magnesium Alcoholates or chlorohydrin and the excessive TiCl in the solution containing the citric acid ester compound shown in logical formula (I)4 Reacted at a temperature of 80-135 DEG C.Preferably, can be TiX by formulan(OR)4-nTitanium compound (R is in formula Carbon number is 1-20 alkyl, and X is halogen, n=1-4；It is preferred that TiCl4) with from formula be MgCl2MROH's adds Compound reacts and prepares ingredient of solid catalyst, and m is 0.1-6 number in formula, and preferably 2 to 3.5, and R is with 1-20 The alkyl of individual carbon atom.Adduct can be conveniently made spherical by the following method：In inertia not miscible with adduct In the presence of hydrocarbon, alcohol and magnesium chloride are mixed, make the rapid chilling of the emulsion, so that adduct is consolidated in the form of spheric granules Change.The spherical MgCl prepared according to the process2MROH adducts example description be found in US4399054 and In US4469648.So obtained adduct directly can react with titanium compound, or it can first pass through thermal control in advance The dealcoholization (80-130 DEG C) of system is to obtain a kind of adduct, and the molal quantity of wherein alcohol is generally below 3, preferably in 0.1-2.5 Between.Can be by the way that adduct (dealcoholysis or itself) be suspended in into cold TiCl4Enter in (general -25-0 DEG C) The reaction of row and titanium compound；Heat the mixture to 80-130 DEG C and kept for 0.5-2 hours at this temperature.Use TiCl4 The processing of progress can be carried out once or repeatedly.With TiCl4Logical formula (I) and (II) can be added during processing Citric acid ester compound is handled, and this processing can be repeated once or repeatedly.
It may include according to a further embodiment of the present invention, the preparation method of the ingredient of solid catalyst, its step：Will Citric acid ester compound shown in anhydrous magnesium chloride and logical formula (I) is ground together under conditions of magnesium dichloride activates. Thus obtained product is at a temperature of 80-130 DEG C with excessive TiCl4Handle one or many.It is molten with hydro carbons after processing Agent washing is until not chloride ion-containing.According to further method, the magnesium dichloride to anhydrous state, titanium compound will be passed through Product obtained from being co-mulled and made into the citric acid ester compound shown in logical formula (I), using such as 1,2- dichloroethanes, The halogenated hydrocarbons of chlorobenzene, dichloromethane etc is handled.The processing is carried out at a temperature of between 40 DEG C to halogenated hydrocarbons boiling point 1-4 hours.Then generally wash to obtain product with the inert hydrocarbon solvent of hexane etc.
According to an embodiment of the present invention, the preparation method of the ingredient of solid catalyst, its step may include：By two Magnesium chloride carries out pre-activate according to known methods, then with excessive TiCl at a temperature of about 80-135 DEG C4Processing, Wherein in the solution containing the citric acid ester compound led to shown in formula (I).Use TiCl4Processing is repeatedly and with hexane to solid Cleaned to remove any unreacted TiCl4。
In addition, the preparation method of ingredient of solid catalyst of the present invention, may further reference disclosed in CN1208045 The preparation method of solids containing titanium catalytic component prepared, i.e.,：First at low temperature, one kind selected from alcohol, phenol, ketone, Aldehyde, ether, amine, pyridine and ester compound in the presence of contact liquid magnesium compound and liquid titanium compound, be settled out solid Body, temperature during contact are generally -70~200 DEG C, are preferably -30~130 DEG C, in contact process shown in logical formula (I) Citric acid ester compound processing.
In addition, the preparation method of ingredient of solid catalyst of the present invention, its step may also include：Magnesium compound is molten In the dicyandiamide solution that Xie Yu is made up of organic epoxy compound thing, organic phosphorus compound and inert diluent, homogeneous solution is formed Mixed afterwards with titanium compound, in the presence of precipitation additive, wash out solids；Lemon of this solids shown in logical formula (I) Lemon ester compound processing, it is carried on solids, if necessary, then with titanium tetrahalide and inert diluent processing and Obtain.Wherein, precipitation additive is one kind in organic acid anhydride, organic acid, ether, ketone.The each component is with every mole of halogen Change magnesium meter, organic epoxy compound thing is 0.2-10 moles, and organic phosphorus compound is 0.1-3 moles, precipitation additive 0.03-1.0 Mole, transition metal Ti halide and its derivative are 0.5-150 moles.
Finally, ingredient of solid catalyst of the present invention, can also use in SiO2, the inorganic oxide such as aluminum oxide or The magnesium compound loaded on porous resin is prepared as carrier, then activated by known method, then about With excessive TiCl at a temperature of 80~135 DEG C4Processing, the citrate having shown in logical formula (I) is added in processing procedure Compound.
Reaction as described above results in the magnesium halide in activated state.In addition to these reactions, prior art can be also used Middle other methods, the magnesium halide in activity morphology is formed using the compound different from magnesium halide as initial substance.
In preparation method as described above, leading to the citric acid ester compound shown in formula (I) can directly be added with itself Enter or carried out by other optional modes, for example, next in situ obtained by using appropriate precursor, physical efficiency exists before this is appropriate In preferable electron donor compound, such as chemical reaction known to such as esterification, ester exchange etc. is relied on to complete to change. Generally, relative to MgCl2For, with 0.01-5, preferably 0.05-2.0 mol ratio uses the lemon shown in logical formula (I) Lemon ester compound.
Another object of the present invention is to provide one kind to be used for alkene CH2The catalyst of=CH polymerizations, wherein, R is hydrogen Or the hydrocarbyl group containing 1-12 carbon atom.The catalyst includes the product that following components reacts to obtain：
Component a, the present invention are as described above containing Mg, Ti and halogen and selected from the citrate shown in logical formula (I) Ingredient of solid catalyst of the compound as internal electron donor；
Component b, at least one formula are AlRnX(3-n)Organo-aluminum compound, R is hydrogen, carbon number 1-20 in formula Alkyl；X is halogen, and n is the integer of 0≤n≤3；Opinion, optionally,
Component c, at least one external donor compound.
Preferably, the organo-aluminum compound may be selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, The trialkyl aluminium compound of tri-n-hexyl aluminum, trioctylaluminum esters.In addition, organo-aluminum compound of the present invention may be used also Using trialkyl aluminium compound and aluminum alkyl halide, alkyl aluminum hydride or such as AlEt2Cl and Al2Et3Cl3Etc The mixture of alkylaluminium sesquichloride, it is possible to use alkylaluminoxane.
Application for needing very high isotacticity, external donor compound also can be used in the catalyst.In this hair In bright, the optional self-drifting of external donor compound is RnSi(OR1)4-nSilicone compounds, R and R in formula1 For C1-C18Alkyl, n is the integer of 0≤n≤3, optionally also hetero atom.
Specifically, in the present invention, formula as described above is RnSi(OR1)4-nSilicone compounds, it include but It is not limited to：Trimethylmethoxysilane, trimethylethoxysilane, three n-propyl methoxy silanes, three n-propyl ethoxies Base silane, three normal-butyl methoxy silanes, triisobutyl Ethoxysilane, thricyclohexyl methyl-monosilane, thricyclohexyl second It is TMOS, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diη-propyl dimethoxysilane, two different Propyldimethoxy-silane, diη-propyl diethoxy silane, diisopropyldiethoxysilane, di-n-butyl diethoxy Base silane, diisobutyl diethoxy silane, di-t-butyl dimethoxysilane, di-t-butyl dimethoxysilane, two Normal-butyl dimethoxysilane, second, isobutyl dimethoxy silane, di-t-butyl diethoxy silane, di-n-butyl diethyl TMOS, n-butylmethyldimethoxyforane, two (2- ethylhexyls) dimethoxysilanes, two (2- ethyl hexyls Base) diethoxy silane, Dicyclohexyldimethoxysilane, dicyclohexyl diethoxy silane, bicyclopentyl dimethoxy Base silane, bicyclopentyl diethoxy silane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl methyl diethoxy silane, Cyclohexyl-ethyl dimethoxysilane, cyclohexyl isopropyl dimethoxysilane, cyclohexyl-ethyl diethoxy silane, ring Phenyl-methyl dimethoxysilane, cyclopentyl ethyl diethoxy silane, cyclopenta isopropyl diethoxy silane, ring penta Base isobutyl group dimethoxysilane, cyclohexyl n-propyl dimethoxysilane, cyclohexyl n-propyl diethoxy silane, ring Hexyl normal-butyl diethoxy silane, phenyl-methyl dimethoxysilane, phenyl-methyl diethoxy silane, amyl group ethyl Dimethoxysilane, amyl group ethyl diethoxy silane, cyclohexyldimethyl methoxy silane, cyclohexyl diethyl methoxy Base silane, cyclohexyl diethylmethoxysilane, cyclohexyl diethylethoxysilane, 2- ethylhexyl trimethoxy silicon Alkane, cyclohexyl dimethoxysilane, cyclohexyl diethoxy silane, 2- ethylhexyls triethoxysilane, ethyl front three TMOS, ethyl triethoxysilane, n-propyl trimethoxy silane, n-propyl triethoxysilane, isopropyl three Methoxy silane, isopro-pyltriethoxysilane, n-butyltrimethoxysilane, trimethoxysilane, tertiary fourth Base trimethoxy silane, ne-butyltriethoxysilaneand, cyclohexyl trimethoxy silane, cyclohexyltriethyloxysilane, Cyclopentyl-trimethoxy-silane, cyclopenta triethoxysilane, vinyltrimethoxy silane, vinyl triethoxyl silicon Alkane, 2- ethylhexyls trimethoxy silane, 2- ethylhexyls triethoxysilane, amyltrimethoxysilane, amyl group three Ethoxysilane, tetramethoxy-silicane, tetraethoxysilane, cyclohexyl ring dicyclopentyldimetoxy silane, cyclohexyl ring penta Base diethoxy silane, cyclohexyl ring amyl group dipropoxy silane, 3- methyl cyclohexane cyclopentyls dimethoxysilane, 4- Methyl cyclohexane cyclopentyl dimethoxysilane, 3,5- dimethyleyelohexane cyclopentyls dimethoxysilane, 3- methyl cyclohexanes Butylcyclohexyl dimethoxysilane, two (3- methylcyclohexyls) dimethoxysilanes, 4- methyl cyclohexane butylcyclohexyl diformazans TMOS, two (4- methylcyclohexyls) dimethoxysilanes, 3,5- dimethyleyelohexane butylcyclohexyls dimethoxysilane, Two (3,5- Dimethylcyclohexyl) dimethoxysilanes, tetrapropoxysilane, four butoxy silanes.In these organosilicons It is preferred in compound：Diη-propyl dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxy silicon Alkane, second, isobutyl dimethoxy silane, di-t-butyl dimethoxysilane, di-n-butyl diethoxy silane, the tert-butyl group Trimethoxy silane, Dicyclohexyldimethoxysilane, dicyclohexyl diethoxy silane, cyclohexyl methyl dimethoxy Silane, cyclohexyl-ethyl diethoxy silane, cyclohexyl-ethyl dimethoxysilane, cyclohexyl-ethyl diethoxy silane, Cyclopentyl-methyl dimethoxysilane, cyclopentyl-methyl diethoxy silane, cyclopentyl ethyl dimethoxysilane, hexamethylene Cyclopentyl dimethoxysilane, cyclohexyl ring amyl group diethoxy silane, 3- methyl cyclohexane cyclopentyl dimethoxy silicon Alkane, 4- methyl cyclohexane cyclopentyl dimethoxysilanes and 3,5- dimethylcyclopentyl dimethoxysilane etc.；And these are changed Compound can be used alone or a variety of be used in mixed way.
Further, present invention formula as described above is RnSi(OR1)4-nSilicone compounds preferably use diisopropyl Base dimethoxysilane；Di-n-butyl dimethoxysilane；Second, isobutyl dimethoxy silane；Diphenyl dimethoxy silicon Alkane；Phenyl triethoxysilane；Methyl-t-butyldimethoxysilane；Dicyclopentyl dimethoxyl silane；2- ethyl piperazines Piperidinyl -2- t-butyldimethoxysilanes and (1,1,1- tri- fluoro- 2- propyl group) -2- ethyl piperidine base dimethoxysilanes and (1, 1,1- tri- fluoro- 2- propyl group)-methyl and methoxy silane, cyclohexyl trimethoxy silane；Tert-butyl trimethoxy silane or Tertiary hexyl trimethoxy silane.
Catalyst as described above of the invention can be used for alkene CH2In=CHR (co) polymerizations, the preferred second of described alkene Alkene, propylene, 1- butylene, 4-methyl-1-pentene, 1- hexenes and 1- octenes.
In order to which the catalyst in the application present invention carries out olefinic polymerization, homopolymerization and copolymerization can be applied as described above by group Divide the catalyst obtained by a, b, c.Generally, component b and component a mol ratio is that 1-1000mol is contained in per mol Titanium atom in component a, preferably 50-800mol are contained in the titanium atom in component a per mol；Component c and component a Mol ratio be 0.002-10, preferably 0.01-2, preferably 0.01-0.5.
In preparation process, the sizing material order of each component is arbitrary, but is added at first in paradigmatic system with component b, so It is optimal to add component c afterwards, be eventually adding component a.
The present invention polymerization technique can have solvent or without solvent in the case of carry out.Olefinic monomer can be gas phase or Liquid phase.Hydrogen can further be added as molecular weight regulator.Certainly polymerization can also be in the feelings of no molecular weight regulator Carried out under condition.Polymerization temperature is not higher than 200 DEG C, preferably 20-100 DEG C, more preferably 40-80 DEG C of temperature.Polymerization pressure 10MPa, preferably 1-5MPa are not exceeded.Continuous polymerization or batch polymerization process can be applied.And polymerisation A step, two steps or multistep can be divided to carry out.
The catalyst of the present invention can be applied, which to carry out homopolymerization or the alkene of copolymerization, to be included：Linear alkene, such as：Ethene, propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- heptene, 1- nonenes, 1- decene；Branched-chain alkene, such as：3-methyl-1-butene and 4- Methyl-1-pentene；Alkadienes is such as：Butadiene, vinylcyclopentene and vinylcyclohexene.Catalyst of the present invention It is preferably applied in polyethylene and polypropylene.These alkene can be independent or a variety of are used in mixed way.
Using the polymerization (herein referring to mass polymerization) of catalytic component a, b, c of present invention alkene carried out, recommend Prepolymerization is carried out to increase the activity of catalyst, the isotacticity of polymer, particle properties etc..The prepolymerization technology equally may be used For styrene homopolymerization.
In prepolymerization technology, the charging sequence of each component and monomer is arbitrary.But contain it is preferred that being first added to component b Have inertia or the alkene gas that will be polymerize in, the one or more alkene to be polymerize then are added after component a is added. During the alkene of application organosilan is prepolymerized, it is proposed that by component b is added to inert gas or to be polymerize In the prepolymerization system of olefin gas, component c is then added, component a is then added, finally adds alkene.
Or of the present invention it is used for alkene CH2The catalyst of=CHR polymerizations, wherein R is for hydrogen or containing 1-12 The hydrocarbyl group of carbon atom, it can also be the product of following component reaction：
Component a, the catalytic component containing Mg, Ti, halogen and internal electron donor；
Component b, at least one formula are AlRnX(3-n)Organo-aluminum compound, R is hydrogen, carbon number 1-20 in formula Alkyl；X is halogen, and n is the integer of 0≤n≤3；And optionally,
Component c, at least one external donor compound, wherein, such as formula may be selected in the external donor compound (I) at least one citric acid ester compound shown in：
Wherein, R1、R2、R3With R as hereinbefore defined.
Wherein, internal electron donor described in component a is selected from the simple function group or multifunctional of at least one ether, ester, ketone or amine Dough compound, or selected from the Lewis alkali containing one or more electronegativity groups, electron donor atom therein be selected from N, O, the group of S, P, As or Sn composition, for example, the electron donor chemical combination selected from two ethers, esters, ketone and amine Thing.
Especially, internal electron donor described in component a is selected from as led at least one citrate chemical combination shown in formula (I) Thing：
Wherein, R1、R2、R3With R as hereinbefore defined.
Especially, in the present invention, the preferred phthalate compound of internal electron donor, 1, the 3- bis- in component a Ether compound, succinate compound compound, 1,3- diol-lipids compound, the citric acid ester compound of logical formula (I). Further, the internal electron donor in component a is preferably 1,3- diether compounds, succinate compound compound, 1,3- The citric acid ester compound of diol-lipid compound or logical formula (I).
According to another embodiment of the invention, a kind of application of catalyst in olefin polymerization as described above is additionally provided.
The beneficial effects of the present invention are citric acid ester compound of the present invention, it is by being deposited extensively in plant And can also the citric acid of a large amount of commercial synthesis be prepared for initiation material, most of citrate, such as：Citric acid Tri-n-butyl, ATBC, citric acid three (2- ethyl hexyls) ester etc., are excellent nontoxic plasticizers, Wherein, ATBC (ATBC) is the generally acknowledged nontoxic plasticizer of countries in the world today, has been entered both at home and abroad Capable various chronic toxicity tests all show：ATBC, no matter acute, chronic or anxious in Asia Property experiment in, all without obvious pathologic process is caused, be considered nontoxic material, be by main flourishing state Family all permits one of a few food packaging nontoxic plasticizer used.In view of acetyl tributyl citrate Hypotoxicity, food and drug administration (FDA) not only ratify its plastics as packaging for foodstuff and medical instruments and increased Agent is moulded, while also ratifies it as food additives (synthetic perfume).The present invention first should as internal electron donor using it Use several big most representational neat lattice such as magnesium ethylate system, chlorination magnesium alcoholate system and magnesium chloride solution modeling system In the preparation system for strangling Natta catalyst, the catalyst of gained, hydrogen regulation performance is good, can prepare the polymerization of wide molecular weight distribution Thing.It is applied to as external electron donor in olefinic polymerization, isotacticity is good.Above all its asepsis environment-protecting, can For the exploitation of foodstuffs without toxicity and the high-end trade mark polyolefin products of medical treatment.In addition citric acid ester type compound is cheap, There is more preferable economic benefit relative to expensive other internal electron donor compounds.
Embodiment
For ease of being further appreciated that to each aspect of the present invention and advantage, below in conjunction with specific embodiment to the present invention's Embodiment is described further.But following embodiments are merely to illustrate the present invention and the non-limiting present invention.
Citric acid ester compound employed in following each embodiments is intended to as example illustrating the present invention, rather than to this Specific restriction is made in invention.It will be apparent to a skilled person that other belong to scope but not following The citric acid ester compound referred in embodiment is each fallen within protection scope of the present invention.
Citric acid ester compound used in various embodiments of the present invention, a part is commercial chemicals, such as, citric acid Trimethyl, triethyl citrate, ATBC, CitroflexA-2, citroflex A-4 etc., Use can directly be bought.Other non-commercial chemicals, a variety of conventional methods, such as provided below one can be passed through Kind prepares the method (reaction 1) of acyl group citrate, is prepared.That is, once or after being esterified by several times obtained by citric acid Corresponding citrate, then with acyl chloride reaction, obtain target product acyl group citrate.Equally, ether citrate Can be by the way that citrate alkylation be prepared.It will be apparent to a skilled person that the preparation method is only Illustrative purpose rather than specific restriction is made to the present invention.Table 1 be citrate example of the present invention and Corresponding structure.
1 citrate of the present invention of table and corresponding structure
The preparation of ingredient of solid catalyst
It should be noted that：The following embodiment for preparing catalyst, carried out under high pure nitrogen protection.It is each specific real Under applying for example：
Embodiment 1
In 5 mouthfuls of flasks with stirring that 500ml is sufficiently displaced from through nitrogen, 10g diethoxies magnesium and 80mL are added Toluene prepares suspension, is maintained at -10 DEG C of dropwise addition titanium tetrachloride 20mL, is to slowly warm up to system after being added dropwise 10 DEG C and titanium tetrachloride 60mL is added dropwise, is to slowly warm up to 90 DEG C again afterwards, add 3g triethyl citrates, Ran Houji It is continuous to be warming up to 120 DEG C of constant temperature 2 hours, it is then that liquid press filtration is clean, filter off liquid, the solid 120mL tetra- of gained Titanium chloride washs 3 times at 125 DEG C.The solid of gained is washed 2 times with 150mL hexanes at 60 DEG C, room temperature washing 2 times, Liquid and drying are filtered off, it is ingredient of solid catalyst to obtain 9.86g solid powders.The Ti content of ingredient of solid catalyst, Internal electron donor content and aggregated data are shown in Table 2.
Embodiment 2-25
Ingredient of solid catalyst preparation method such as embodiment 1, difference are to replace triethyl citrate in order respectively For the compound in table 1.
Embodiment 26
In 5 mouthfuls of flasks with stirring that 500ml is sufficiently displaced from through nitrogen, 10gMgCl is added2·3C2H5OH is micro- Ball and 150mL titanium tetrachlorides prepare suspension, are maintained at -15 DEG C 1 hour, are slowly warming up to 80 DEG C, add 2.5g Citroflex A-4, then proceedes to be warming up to 110 DEG C of constant temperature 1 hour, and liquid press filtration is clean, filters off liquid, The solid of gained is washed 3 times with 120mL titanium tetrachlorides at 125 DEG C.The solid of gained is washed with 150mL hexanes at 60 DEG C Wash 4 times, filter off liquid and drying, produce ingredient of solid catalyst.Its corresponding performance data is as shown in table 2.
Embodiment 27
Anhydrous magnesium chloride 8g, 38mL decane and 35mL 2-Ethylhexyl Alcohol react 2 hours to be formed at 130 DEG C Even solution.1.7g phthalic anhydrides are added in solution, mixture stirs 1 hour at 130 DEG C, so that adjacent benzene two Formic anhydride is dissolved completely in homogeneous solution.Obtained homogeneous solution is cooled to room temperature, and holding was added drop-wise in 1 hour In -20 DEG C of 200mL titanium tetrachlorides；Drip rear mixed solution and 110 DEG C were heated in 4 hours, when temperature reaches 3g citroflex A-4s are added at 110 DEG C, mixture stirs 2 hours at the temperature disclosed above.Reaction 2 hours Afterwards, solid portion is collected by heat filtering.Solid portion is suspended in 275mL titanium tetrachlorides, and in 110 DEG C of conditions Lower reaction 2 hours.After the completion of reaction, solids portion is collected by heat filtering, and decane and hexane are used at 110 DEG C Fully washed, ingredient of solid catalyst is obtained after draining.Table 2 shows its corresponding performance data.
Embodiment 28
In 5 mouthfuls of flasks with stirring that 500ml is sufficiently displaced from through nitrogen, add at room temperature 10g anhydrous magnesium chlorides, 150mL toluene, 17mL epoxychloropropane and 16mL tributyl phosphates, stirring are warming up to 50 DEG C and maintained 2 hours It is completely dissolved to solid, then adds 2.40g phthalic anhydrides, then maintain 1 hour.Solution is cooled to -25 DEG C, 110mL titanium tetrachlorides were added dropwise in 1 hour, is to slowly warm up to 80 DEG C, in temperature-rise period, progressively washes out solids. 3g citroflex A-4s are added, are maintained 1 hour at 80 DEG C.Washed twice after filtering with 200mL toluene, Then 120mL toluene and 80mL titanium tetrachlorides are added, continues to be warming up to 110 DEG C, constant temperature 2 hours, then by liquid Press filtration is clean, repeats processing once.Liquid is filtered off, the solid of gained is washed 1 time with 100mL dichloroethanes, oneself Alkane is washed 4 times, and ingredient of solid catalyst is obtained after drying.Its corresponding performance data is as shown in table 2.
Embodiment 29
Ingredient of solid catalyst preparation method such as embodiment 1, difference are that 3g triethyl citrates are replaced with into 1g lemons Lemon acid tributyl and 2g citroflex A-4s.
Embodiment 30
Ingredient of solid catalyst preparation method such as embodiment 1, difference are that 3g triethyl citrates are replaced with into 1g lemons Lemon acid tributyl methyl ether and 2g citroflex A-4s.
Comparative example 1
Ingredient of solid catalyst preparation method such as embodiment 1, difference are triethyl citrate replacing with adjacent benzene two Formic acid di-n-butyl.
Comparative example 2
Ingredient of solid catalyst preparation method such as embodiment 26, difference are to replace citroflex A-4 For n-butyl phthalate.
Comparative example 3
Ingredient of solid catalyst preparation method such as embodiment 27, difference are to replace citroflex A-4 For n-butyl phthalate.
Comparative example 4
Ingredient of solid catalyst preparation method such as embodiment 28, difference are to replace with citroflex A-4 N-butyl phthalate.
Polymerization
Carried out using obtained solid catalyst in embodiment 1-25 and comparative example 1-4 as the component of olefin polymerization catalysis Polymerization evaluation：
The polymerization process is：In 5L stainless steel cauldrons after nitrogen is sufficiently displaced from, it is 0.5 to add 5mL concentration Mol/L triethyl aluminum hexane solution and 1mL concentration is 0.1mol/L Cyclohexylmethyldimethoxysilane (CMMS) Hexane solution and the catalyst 10mg of preparation, then add 10mL hexanes and rinse charge line, add 2L (marks Under quasi- state) hydrogen, and 2.5L refines propylene, and control reaction is warming up to 70 DEG C in 20 DEG C of pre-polymerizations 5 minutes, warm herein The lower polymerisation of degree 1 hour.After reaction terminates, reactor is cooled and stops stirring discharge reaction product, through being dried to obtain Polymer.(bulk density of polymer is determined using JB/T 2412-2008 methods)
The ingredient of solid catalyst polymerization data of table 2
It can be seen from the polymerization data of table 2, using citric acid ester type compound as internal electron donor, using four kinds Catalyst obtained by different catalyst preparation process, during for propylene polymerization, polyacrylic point obtained by all samples Son amount distribution is more wider than the polypropylene obtained by phthalate catalyst.
The aggregated data of the comparative example 1 of table 3 and embodiment 5, embodiment 8 and embodiment 9
Table 3 shown in the case where added hydrogen changes, comparative example 1 and embodiment 5, embodiment 8 and real Apply the aggregated data of example 9.It can be seen from the data in table 3, the catalyst using citric acid ester compound as internal electron donor It is polymerize, with the increase of added hydrogen, polyacrylic melt index significantly increases, and illustrates that the catalyst system and catalyzing hydrogen is adjusted Sensitiveness is good；And there is more sensitive hydrogen to adjust compared to phthalic acid ester.
Embodiment 31
Obtained solid catalyst carries out polymerization evaluation as the component of olefin polymerization catalysis using in comparative example 1：
In 5L stainless steel cauldrons after nitrogen is sufficiently displaced from, add triethyl aluminum that 5mL concentration is 0.5mol/L oneself Alkane solution and the hexane solution of citroflex A-4 and the catalyst 10 of preparation that 2mL concentration is 0.1mol/L Mg, then add 10mL hexanes and rinse charge line, add 2L (under standard state) hydrogen, and 2.5L refined third Alkene, control reaction are warming up to 70 DEG C, at this temperature polymerisation 1 hour in 20 DEG C of pre-polymerizations 5 minutes.Reaction terminates Afterwards, reactor is cooled and stops stirring discharge reaction product, through being dried to obtain polymer.(bulk density of polymer uses JB/T 2412-2008 methods determine).Its aggregated data is as shown in table 4.
Embodiment 32
Ingredient of solid catalyst preparation method such as embodiment 1, difference are triethyl citrate replacing with 9,9- pairs Methoxyl methyl fluorenes.Polymerization evaluation condition such as embodiment 31.Its corresponding performance data is as shown in table 4.
Embodiment 33
Ingredient of solid catalyst preparation method such as embodiment 1, difference are triethyl citrate replacing with 2,3- bis- Isopropyl diethyl succinate.Polymerization evaluation condition such as embodiment 31.Its corresponding performance data is as shown in table 4.
Embodiment 34
Ingredient of solid catalyst preparation method such as embodiment 1, difference are triethyl citrate replacing with 2,4- penta Bisbenzoate.Polymerization evaluation condition such as embodiment 31.Its corresponding performance data is as shown in table 4.
Embodiment 35
The ingredient of solid catalyst prepared using embodiment 1, polymerization evaluation condition such as embodiment 31.Its corresponding performance Data are as shown in table 4.
Embodiment 36
Ingredient of solid catalyst preparation method such as embodiment 1, difference are triethyl citrate replacing with 9,9- pairs Methoxyl methyl fluorenes.Polymerization evaluation condition such as embodiment 31, difference are citroflex A-4 replacing with second Acyl group trimethyl citrate.Its corresponding performance is as shown in table 4.
Embodiment 37
Ingredient of solid catalyst preparation method such as embodiment 1, difference are triethyl citrate replacing with 9,9- pairs Methoxyl methyl fluorenes.Polymerization evaluation condition such as embodiment 31, difference are citroflex A-4 replacing with second Acyl triethyl citrate.Its corresponding performance is as shown in table 4.
Comparative example 5
Ingredient of solid catalyst preparation method such as embodiment 30.First of the 1mL concentration for 0.1mol/L is used in polymerization evaluation Butylcyclohexyl dimethoxysilane (CMMS) hexane solution.
Comparative example 6
Ingredient of solid catalyst preparation method such as embodiment 30, external electron donor is not used in polymerization evaluation.
The polymerization of table 4 is evaluated
It can be seen from the polymerization data of table 4, the catalyst using citric acid ester compound as external electron donor is gathered Close, can with high activity obtain high isotactic polymer.It can be seen that by comparative example 6：Using the double methoxyl methyl fluorenes of 9,9- as The catalyst of internal electron donor activity when without using external electron donor is up to 80.3Kg/gCath-1, but isotacticity is relatively low, Need to add external electron donor to improve isotacticity.After CMMS external electron donors being used it can be seen from comparative example 5, Isotacticity is improved, but activity is significantly reduced to 55.6Kg/gCath-1.Using citroflex A-4 as outer to electricity Daughter, embodiment 30 can obtain high isotatic polypropylene, and activity still keeps 70.6Kg/gCath-1High level. Moreover, according to other several embodiments it is also seen that being had using citrate relative to CMMS external electron donor activity aobvious Write and improve, while keep high isotactic.
The present invention has carried out detailed explanation by preferred embodiment.However, by studying carefully above, to each Apparent to the change of embodiment and increase and those of ordinary skill in the art.It is it is intended that all These changes and increase fall in the protection domain of the claims in the present invention.
Term used herein is only that specific embodiment is illustrated, and is not intended to and limits the invention.Remove It is non-defined otherwise, all terms (including technical term and scientific terminology) used herein with art of the present invention Those skilled in the art understanding it is identical.Must also it is clear that, except herein have clearly definition in addition to, in such as dictionary The term generally defined should be construed in the linguistic context of this specification and correlation technique can have the consistent meaning, without The idealization that should be explained or undue formalization.

Claims (18)

1. a kind of ingredient of solid catalyst for olefinic polymerization, it contains Mg, Ti, halogen and internal electron donor, its It is characterised by：The internal electron donor is selected from as led at least one of citric acid ester compound shown in formula (I)：
Wherein, R1、R2And R3For C that is identical or differing1-C20Alkyl；R is hydrogen, or is C1-C20Hydrocarbon Base, or be C2-C21Acyl group.
2. ingredient of solid catalyst according to claim 1, it is characterised in that：R1、R2And R3Independently of one another Selected from C1-C20Straight chain, C1-C20Branched alkyl, C1-C20Alkenyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20 Alkaryl or C7-C20Aryl；Preferably, R1、R2And R3It is independently from each other methyl, ethyl, propyl group, different Propyl group, butyl, the tert-butyl group, isobutyl group, amyl group, cyclopenta, neopentyl, hexyl, cyclohexyl, heptyl, octyl group, Nonyl, decyl, undecyl~eicosyl, the alkenyl less than 20 carbon, ester group, phenyl, alkyl phenyl, phenyl Alkyl, indenyl, benzyl, halo or the cycloalkyl substituted by hetero atom N, O, S, P, Si, Ge, phenyl, alkyl Phenyl, phenylalkyl, indenyl, benzyl；Or selected from heterocyclic aryl substituent.
3. ingredient of solid catalyst according to claim 1, it is characterised in that：R1、R2And R3It is bonded to mutually Ring.
4. ingredient of solid catalyst according to claim 1, it is characterised in that：When the R is C1-C20Hydrocarbon During base, it is selected from C1-C20Straight chain, C1-C20Branched alkyl, C1-C20Alkenyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl or C7-C20Aryl；Preferably, the R be selected from methyl, ethyl, propyl group, isopropyl, butyl, The tert-butyl group, isobutyl group, amyl group, cyclopenta, neopentyl, hexyl, cyclohexyl, heptyl, octyl group, nonyl, decyl, Undecyl~eicosyl, the alkenyl less than 20 carbon, ester group, phenyl, alkyl phenyl, phenylalkyl, indenyl, Benzyl, halo or the cycloalkyl substituted by hetero atom N, O, S, P, Si, Ge, phenyl, alkyl phenyl, octadecyloxy phenyl Base, indenyl, benzyl；Or selected from heterocyclic aryl substituent.
5. ingredient of solid catalyst according to claim 1, it is characterised in that：When the R is C2-C21Acyl During base, the citric acid ester compound has as led to the structure shown in formula (II)：
Wherein, R4For C1-C20Alkyl.
6. ingredient of solid catalyst according to claim 5, it is characterised in that：The R4Selected from C1-C20Straight chain, C1-C20Branched alkyl, C1-C20Alkenyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl or C7-C20Virtue Alkyl；Preferably, the R4Selected from methyl, ethyl, propyl group, isopropyl, butyl, the tert-butyl group, isobutyl group, amyl group, It is cyclopenta, neopentyl, hexyl, cyclohexyl, heptyl, octyl group, nonyl, decyl, undecyl~eicosyl, few In the alkenyl of 20 carbon, ester group, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl, halo or by hetero atom N, O, the cycloalkyl of S, P, Si, Ge substitution, phenyl, alkyl phenyl, phenylalkyl, indenyl, benzyl；Or it is selected from Heterocyclic aryl substituent.
7. according to the ingredient of solid catalyst described in any one in claim 1-6, it is characterised in that：It includes titanium Compound, magnesium compound and the reaction product selected from the citric acid ester compound as shown in logical formula (I), wherein, the magnesium The precursor of compound is selected from：XnMg(OR)2-n, MgCl2MROH, R2-nMgXn, MgCl2/SiO2, MgCl2/Al2O3, Or at least one of mixture of magnesium halide and alcohol titanium, m is 0.1-6 number in formula, and 0≤n≤2, X are halogen, R For hydrogen or C1-C20Alkyl；The formula of the titanium compound is TiXN(OR)4-N, R is that carbon number is 1-20 in formula Alkyl, X is halogen, N=0-4.
8. a kind of preparation method of the ingredient of solid catalyst as claimed in claim 7 for olefinic polymerization, its feature It is：Its preparation process includes：Make magnesium compound and titanium compound with being selected from as led to the citrate chemical combination shown in formula (I) Thing contacts, so as to obtain ingredient of solid catalyst.
9. preparation method according to claim 8, it is characterised in that：The magnesium compound is magnesium dihalide or two The derivative that at least one halogen atom is replaced by oxyl or halo oxyl in magnesium halide molecular formula.
10. preparation method according to claim 9, it is characterised in that：The magnesium compound is alkoxyl magnesium or virtue Epoxide magnesium；Or the alcohol adduct that the magnesium compound is magnesium dihalide；Or the magnesium compound is to be selected from one kind Alcohol, phenol, ketone, aldehyde, ether, amine, pyridine and ester compound in the presence of make general formula R2-nMgXnLiquid magnesium compound The solid of reprecipitation precipitation is contacted with liquid titanium compound.
11. one kind is used for alkene CH2The catalyst of=CHR polymerizations, wherein R is hydrogen or the hydrocarbon containing 1-12 carbon atom Base group, it is characterised in that the catalyst includes the product of following components reaction：
Ingredient of solid catalyst in component a, claim 1-7 described in any one；
Component b, at least one formula are AlRnX(3-n)Organo-aluminum compound, R is hydrogen, carbon number 1-20 in formula Alkyl；X is halogen, and n is the integer of 0≤n≤3；And optionally,
Component c, at least one external donor compound.
12. catalyst according to claim 11, it is characterised in that：The organo-aluminum compound is trialkylaluminium Compound, preferably trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum or trioctylaluminum.
13. catalyst according to claim 11, it is characterised in that：The external donor compound is selected from logical Formula is RnSi(OR1)4-nSilicone compounds, R and R in formula1For C1-C18Alkyl, optional also hetero atom；n For the integer of 0≤n≤3.
14. one kind is used for alkene CH2The catalyst of=CHR polymerizations, wherein R is hydrogen or the hydrocarbon containing 1-12 carbon atom Base group, it is characterised in that the catalyst includes the solid catalyst group as described in any one in claim 1-7 Divide and the prepolymer obtained by alkene progress prepolymerization.
15. one kind is used for alkene CH2The catalyst of=CHR polymerizations, wherein R is hydrogen or the hydrocarbon containing 1-12 carbon atom Base group, it is characterised in that the catalyst includes the product of following components reaction：
Component a, the ingredient of solid catalyst containing Mg, Ti, halogen and internal electron donor；
Component b, at least one formula are AlRnX(3-n)Organo-aluminum compound, R is hydrogen, carbon number 1-20 in formula Alkyl；X is halogen, and n is the integer of 0≤n≤3；And optionally,
Component c, at least one external donor compound, wherein, the external donor compound is selected from such as logical formula (I) Shown citric acid ester compound：
Wherein, R1、R2And R3For C that is identical or differing1-C20Alkyl；R is hydrogen, or is C1-C20Hydrocarbon Base, or be C2-C21Acyl group.
16. catalyst according to claim 16, it is characterised in that：The internal electron donor is selected from least one Ether, ester, the simple function group or polyfunctional compound of ketone or amine, or selected from containing one or more electronegativity groups Lewis alkali, electron donor atom therein are selected from the group of N, O, S, P, As or Sn composition.
17. catalyst according to claim 16, it is characterised in that：The internal electron donor is selected from such as logical formula (I) Shown citric acid ester compound：
Wherein, R1、R2And R3For C that is identical or differing1-C20Alkyl；R is hydrogen, or is C1-C20Hydrocarbon Base, or be C2-C21Acyl group.
18. the application of catalyst in olefin polymerization as described in any one in claim 11 or 14 or 15.
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