CN112645972A - Method for preparing modified alkylaluminoxane - Google Patents
Method for preparing modified alkylaluminoxane Download PDFInfo
- Publication number
- CN112645972A CN112645972A CN201910963144.XA CN201910963144A CN112645972A CN 112645972 A CN112645972 A CN 112645972A CN 201910963144 A CN201910963144 A CN 201910963144A CN 112645972 A CN112645972 A CN 112645972A
- Authority
- CN
- China
- Prior art keywords
- reaction
- water
- aluminum
- solution
- aryloxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 149
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 150000002989 phenols Chemical class 0.000 claims abstract description 29
- -1 aryloxy-modified alkyl aluminum compound Chemical class 0.000 claims abstract description 20
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 14
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 11
- 230000005540 biological transmission Effects 0.000 claims description 7
- 239000012429 reaction media Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 23
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 15
- 230000007062 hydrolysis Effects 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000036571 hydration Effects 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- VYNCPPVQAZGELS-UHFFFAOYSA-N toluene;trimethylalumane Chemical compound C[Al](C)C.CC1=CC=CC=C1 VYNCPPVQAZGELS-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000005160 aryl oxy alkyl group Chemical group 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000008358 core component Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
- C07F5/068—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage) preparation of alum(in)oxanes
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention discloses a method for preparing modified alkylaluminoxane, which comprises the following steps: step S1, pre-reacting alkyl aluminum with a phenolic compound to obtain an aryloxy-modified alkyl aluminum compound; step S2, thinning and dispersing the reaction water to below 10 microns through a dispersion and release device; and step S3, controlling the release process of the dispersed reaction water, inputting the reaction water into a reaction system to contact and react with the aryloxy alkylaluminum solution to obtain the aryloxy modified alkylaluminoxane solution. The method reduces the reactivity of the alkyl aluminum through pre-modification, realizes high dispersion of water in a reaction system, has mild reaction conditions and safe and controllable production process, greatly reduces the possibility of over-hydrolysis reaction, and the obtained product has higher activity and stability.
Description
Technical Field
The invention relates to preparation of a polyolefin cocatalyst, in particular to a method for preparing modified alkylaluminoxane.
Background
The alkyl aluminoxane is an important cocatalyst of a polyolefin catalyst, can be combined with a metallocene catalyst or a late transition metal catalyst to catalyze olefin polymerization or copolymerization to produce a series of high-end polyolefin materials with precise and adjustable microstructures and excellent performance, and plays an important role in the development of the polyolefin industry.
The alkyl aluminoxane can be mainly prepared by partial hydrolysis of alkyl aluminum, and because the alkyl aluminum is very active and reacts violently with water, how to effectively control the reaction process becomes the research focus of the preparation process. The existing research mainly focuses on the aspects of the introduction mode of reaction water, the improvement of the preparation process and the like, and accordingly, the preparation method can be divided into two categories, namely a hydrolysis method and a non-hydrolysis method.
The hydrolysis method is to generate alkyl aluminoxane by the reaction of alkyl aluminum and water, and can be divided into an indirect hydrolysis method and a direct hydrolysis method according to the state of water for reaction. The indirect hydration method mainly adopts inorganic salt containing crystal water or porous substance adsorbing water to react with aluminum alkyl, and the commonly used crystal hydrate comprises CuSO4·5H2O、FeSO4·7H2O、Al2(SO4)3·18H2O、LiBr·2H2O, and the like. The main problems of the process are that the surface of inorganic salt used as a carrier of water can adsorb a part of generated aluminoxane products, the effective separation is difficult, the yield of target products is low overall, and the loss of active aluminum is large. The direct hydration method is to control certain technological conditions and introduce water in gas, liquid or solid state into the reactor to react with alkyl aluminum. Due to the fact thatThe direct reaction of the two is very violent, and when the direct hydration method is adopted, some special designs are often needed to be made on reaction equipment, which has higher requirements on reaction control and a synthesis device. However, the direct hydration process is higher than the indirect hydration process in terms of product yield.
In order to avoid severe hydrolysis reactions, researchers from Akzo Nobel developed non-hydrolytic processes involving aluminum alkyls with compounds containing carbon-oxygen bonds (e.g., CO)2Benzoic acid, etc.) to form a primary product, which is subsequently converted to an aluminoxane by means of heat or catalysis, etc. The method has the advantages that the reaction process is controllable, but some byproducts which are difficult to separate are inevitably generated, and the product is not applicable to all single-active-center catalytic systems, so that the method cannot directly replace alkyl aluminoxane prepared by a hydrolysis method in industrial production.
In general, the direct hydration process is currently preferred for large-scale production of ubiquitous, highly efficient alkylaluminoxanes. However, from the viewpoint of improving the safety of the production process and the yield of the product, a key technical difficulty still to be solved at present is how to realize high dispersion of water, and prevent the consequences that the composition and the performance of a target product are affected by local over-reaction or incomplete reaction caused by uneven concentration distribution of water in the reaction process.
On the other hand, it is also possible to achieve effective control of the hydrolysis reaction process by reducing the reactivity of the aluminum alkyl. Partial alkyl is replaced by a group with lower activity, so that the activity and hydrolysis reaction rate of the alkyl aluminum can be effectively reduced, the hydrolysis process is milder and more controllable, and the introduction of a proper group can adjust the structure and Lewis acidity of an alkyl aluminoxane product, and the catalytic activity and stability of the alkyl aluminoxane product are improved. Therefore, the development of a modified alkylaluminoxane based on the modification of an alkylaluminum is attracting attention and attention.
Disclosure of Invention
In order to solve the problems in the existing alkyl aluminoxane preparation technology, the invention provides a method for preparing modified alkyl aluminoxane, which combines the modification of alkyl aluminum and the high dispersion of reaction water, so that the hydrolysis process is mild and controllable, the occurrence of excessive hydrolysis reaction is effectively reduced, and the yield of target products is high.
According to an aspect of the present invention, there is provided a method for preparing a modified alkylaluminoxane, comprising the steps of:
step S1, pre-reacting alkyl aluminum with a phenolic compound to obtain an aryloxy-modified alkyl aluminum compound;
step S2, thinning and dispersing the reaction water to below 10 microns through a dispersion and release device;
and step S3, controlling the release process of the dispersed reaction water, inputting the reaction water into a reaction system to contact and react with the aryloxy alkylaluminum solution to obtain the aryloxy modified alkylaluminoxane solution.
In step S1 of the present invention, the aluminum alkyl has the general formula of AlRnX3-nWherein, R is alkyl, X is one or more selected from aryl, alkoxy and halogen, and n is 1-3.
According to a preferred embodiment of the invention, the aluminum alkyl is a trialkyl aluminum having the general formula AlR3Wherein R is C1-C10Alkyl groups of (a); preferably, R is C1-C4An alkyl group; more preferably, the alkyl aluminum is one or more of trimethyl aluminum, triethyl aluminum and triisobutyl aluminum.
In step S1 of the present invention, the phenolic compound is selected from one or more of phenol, mono-or poly-hydrocarbyl-substituted phenol, mono-or poly-halogen-substituted phenol, mono-or poly-nitrophenol, polyhydric phenol, biphenol, and phenolic hydroxyl group-containing aromatic compounds containing a plurality of different types of substituents.
According to a preferred embodiment of the present invention, in step S1, the phenolic compound is selected from one or more of phenol, mono-or polyalkyl-substituted phenol, mono-or polyphenyl-substituted phenol, mono-or polyhalo-substituted phenol, phenol containing alkyl and halogen substituents, phenol containing phenyl and halogen substituents, biphenol, and polyhydric phenol.
According to a preferred embodiment of the present invention, in step S1, the ratio of the amount of the phenolic compound to the amount of the aluminum alkyl is 0.01 to 1.0, preferably 0.1 to 1.0, and more preferably 0.1 to 0.5, in terms of the ratio of the number of phenolic hydroxyl groups to the number of aluminum atoms.
In step S1 of the present invention, the phenolic compound can make part of the alkyl groups substituted by the corresponding aryloxy groups by reacting the active hydrogen on the phenolic hydroxyl group with the alkyl groups of the aluminum alkyl. In the hydrolysis reaction, the reactivity of the aryloxy group is obviously weaker than that of the alkyl group, so the pre-modification strategy can reduce the reactivity of the alkyl aluminum, and the alkyl aluminum can perform more mildly and controllably in the reaction with water. The value range of the mass ratio of the phenolic compound to the aluminum alkyl can satisfy that after partial alkyl is substituted, the residual alkyl is still enough to participate in further hydrolysis reaction to obtain a proper aluminoxane structure. In addition, the aryloxy group introduced has the same hetero atom, i.e., oxygen atom, as the aluminoxane, and thus has good compatibility with the aluminoxane structure. In the hydrolysis reaction, oxygen in the aryloxy can participate in the construction of structural units of aluminoxane such as Al-O-Al and the like to form aryloxy aluminoxane with high stability, so that the aryloxy is tightly bonded on the aluminoxane.
In step S2 of the present invention, the reaction water is selected from, but not limited to, liquid water, water vapor, an emulsion of water and an inert solvent, a solution of water and a polar solvent, a mixed gas of water vapor and an inert gas, and the like. When the reaction water is dispersed, the reaction water is cut and dispersed through a nano/micron-level or molecular-level dispersion and release device, the core component of the dispersion and release device is selected from but not limited to a micro-sieve pore array, a capillary or capillary array, a membrane material and the like, and the pore diameter of the micro-sieve pore, the inner diameter of the capillary or the inner diameter of a transmission channel of the membrane material are not more than 10 microns, preferably not more than 1 micron.
According to a preferred embodiment of the present invention, in step S2, the molecular-scale dispersion of the reaction water is performed using a membrane material having a transport channel inner diameter of not more than 100nm, preferably not more than 10nm, and more preferably not more than 2 nm. Specifically, the membrane material is an organic, inorganic or organic/inorganic composite membrane material, and for example, advanced membrane materials having an angstrom to nanometer pore inner diameter, such as a molecular sieve membrane, a carbon nanotube membrane, a graphene membrane, and the like, can be selected as a core component of the dispersion release device.
According to a preferred embodiment of the present invention, the reaction water dispersion releasing apparatus further includes a supporting member and a fixing member for the core member, in addition to the core member.
According to a preferred embodiment of the present invention, the reaction water may be dispersed by a dispersion release device in a pressurized manner.
In step S3 of the present invention, the reaction water dispersion and release process is controlled by controlling the conditions of the reaction water form, the transmission temperature, the transmission pressure (driving force), the number and size of transmission channels, the film material thickness or the film material area, etc., and then the reaction water after being finely dispersed is fed into a tank reactor containing an aryloxy alkyl aluminum solution or a tubular/loop type continuous flow reactor using the aryloxy alkyl aluminum solution as a main fluid to perform a contact reaction, thereby obtaining an aryloxy modified alkylaluminoxane solution.
According to the preferred embodiment of the invention, the reactor can be externally applied with one or more of a high gravity field, an ultrasonic field, an electric field or a magnetic field, or multiple reactors can be combined in a series and/or parallel manner, and the reaction water dispersion release device can be installed in one or more of the multiple reactors in series and/or parallel.
According to a preferred embodiment of the present invention, the micromesh array, the capillary or capillary array, the membrane material, etc. are directly contacted with the principal fluid of the aryloxyalkyl aluminum solution or the aryloxyalkyl aluminum solution at one side of the reaction system to facilitate the reaction water to be directly mixed into the reaction system after passing through the transmission channel, and more preferably, an ultrasonic dispersion device or a mechanical emulsification device can be added on the tank reactor or the reaction pipeline near the input of the reaction water to facilitate the further dispersion of the reaction water in the reaction system.
According to a preferred embodiment of the present invention, the concentration by mass of the aryloxyalkyl aluminum in the solution of the aryloxyalkyl aluminum at the beginning of the reaction in step S3 is 1 to 40%, preferably 1 to 20%.
According to a preferred embodiment of the present invention, the aryloxyalkyl aluminum solution is a solution of an aryloxyalkyl aluminum with an inert reaction medium.
According to a preferred embodiment of the invention, the inert reaction medium is an aromatic or aliphatic hydrocarbon, preferably C6-C10Aromatic hydrocarbons, preferably selected from one or more of benzene, toluene, xylene and ethylbenzene.
In a preferred embodiment of the invention, the inert reaction medium is toluene.
According to a preferred embodiment of the present invention, the ratio of the amount of water to the amount of the substance of the aryloxyalkyl aluminum at the time of the contact reaction is 0.1 to 1.0, preferably 0.1 to 0.9, more preferably 0.5 to 0.8.
According to a preferred embodiment of the present invention, in the step S1, the pre-reaction temperature is-50 to 50 ℃, preferably-20 to 30 ℃.
According to a preferred embodiment of the present invention, in the step S3, the temperature of the contact reaction is-50 to 100 ℃, preferably-30 to 50 ℃.
According to a preferred embodiment of the present invention, in the steps S1 and S3, the reaction process may be a constant temperature reaction or a step temperature reaction.
According to a preferred embodiment of the present invention, the method further comprises step S4 of filtering the aryloxy modified alkylaluminoxane solution and concentrating to remove part or all of the solvent to obtain a concentrated aryloxy modified alkylaluminoxane solution or a corresponding solid, wherein the concentration is performed by distillation under reduced pressure or evaporation in an evaporator, preferably, the temperature of the distillation under reduced pressure or the evaporator is not higher than 60 ℃.
Has the advantages that:
the method for preparing the modified alkylaluminoxane provided by the invention is simple and feasible and is flexible to operate. Firstly, modifying the raw material of alkyl aluminum by adopting a phenolic compound, and effectively reducing the reaction activity and the reaction rate when the raw material of alkyl aluminum is contacted with water subsequently; secondly, through the high dispersion of water, the mass transfer and the diffusion of water in the reaction solution can be greatly promoted, the contact reaction efficiency is obviously improved, and the occurrence of the conditions of excessive hydrolysis and the like caused by uneven local concentration of water is effectively reduced.
The invention starts from two raw materials in the reaction process, so that the hydrolysis reaction process is safer and controllable, and the product yield is high. Meanwhile, the modified alkylaluminoxane has better stability, and the existence of aryloxy can hinder the interaction and condensation among alkylaluminoxane molecules and avoid the molecular weight from further increasing to form gel precipitation.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
Example 1
A round hole with the diameter of 1cm is arranged at the position where the side wall of a 250mL reaction kettle is flush with a mechanical stirring paddle and is connected with a section of stainless steel pipe which is inclined upwards at an angle of 45 degrees with the kettle body, a stainless steel thin plate with uniformly distributed micro-sieve pores is arranged at an orifice, and the aperture of each micro-sieve pore is 10 mu m. The reaction kettle is provided with a nitrogen inlet, an air release valve and a cooling jacket, 100mL of trimethylaluminum toluene solution (10 wt%) is added into the reaction kettle under the protection of nitrogen, and the temperature of the reaction kettle is controlled to be 0 ℃. A certain amount of distilled deionized water is filled in a stainless steel tube to ensure that the [ H ] is2O]/[Al]The molar ratio was 0.7, nitrogen gas was introduced into the other end of the steel tube, and the temperature of the reaction water in the stainless steel tube was controlled to 5 ℃.
Starting the reaction, the trimethylaluminum solution is first stirred at 500rpm and a quantity of phenol is slowly added to pre-react with it, [ -OH ]]/[AlMe3]The molar ratio is 0.1 and the reaction time is 0.5 h.
After the pre-reaction is finished, the reaction water slowly enters the reaction kettle through the micro-sieve pore array for contact reaction by adjusting the micro-positive pressure of the nitrogen. After the reaction water is completely input into the reaction kettle, slowly raising the temperature to 30 ℃, and continuously stirring for reaction for 1 hour.
After the reaction is finished, the discharged reaction solution is filtered by a sand core funnel and then subjected to pressure reduction to remove toluene, so that a modified methylaluminoxane product is obtained, and the yield is 67%.
Example 2
This example differs from example 1 in that: the hole opening is embedded with a sand core, and the aperture of the sand core is 2-4 mu m.
The other reaction procedures, conditions and apparatus parameters were the same as those in example 1. The yield of modified methylaluminoxane obtained after the reaction was over was 69%.
Example 3
A stainless steel pipe with the inner diameter of 1cm is inserted into the top of a 250mL reaction kettle, the pipe end is close to the upper part of the stirring paddle, a screen is fixed at the pipe end as a support body, a molecular sieve membrane is arranged on the screen in the pipe, and the average pore diameter is 0.5 nm. The reaction kettle is provided with a nitrogen inlet, an air release valve and a cooling jacket, 100mL of trimethylaluminum toluene solution (10 wt%) is added into the reaction kettle under the protection of nitrogen, and the temperature of the reaction kettle is controlled to be 5 ℃. A certain amount of distilled deionized water is filled in a stainless steel tube to ensure that the [ H ] is2O]/[Al]The molar ratio was 0.7, and nitrogen was passed through the other end of the steel tube.
Starting the reaction, the trimethylaluminum solution is first stirred at 500rpm and a quantity of phenol is slowly added to pre-react with it, [ -OH ]]/[AlMe3]The molar ratio is 0.1 and the reaction time is 0.5 h.
After the pre-reaction is finished, the reaction water slowly enters the reaction kettle through the molecular sieve membrane for contact reaction by adjusting the micro-positive pressure of the nitrogen. After the reaction water is completely input into the reaction kettle, slowly raising the temperature to 30 ℃, and continuously stirring for reaction for 1 hour.
After the reaction is finished, the discharged reaction liquid is filtered by a sand core funnel and then subjected to pressure reduction to remove toluene, so that a modified methylaluminoxane product is obtained, and the yield is 74%.
Example 4
This example differs from example 3 in that: and a graphene film is arranged on the screen in the pipe, and the average interlayer distance of the graphene is 0.4 nm.
Other reaction procedures, conditions and apparatus parameters were the same as those in example 3. The yield of modified methylaluminoxane obtained after the reaction was over was 75%.
Example 5
The outlet pipeline at the bottom of the 250mL reaction kettle is connected with an online emulsification pump, and the outlet pipeline of the pump returns to the reaction kettle from the top of the kettle to form the external circulation of the materials. A branch pipe is arranged on a pipeline close to the inlet of the emulsifying pump, a stainless steel sheet with evenly distributed micro-sieve pores is arranged at the joint of the pipe end of the branch pipe and the main pipeline, and the aperture of the micro-sieve pores is 10 mu m. The reaction kettle is provided with a nitrogen inlet, an emptying valve and a cooling jacket,under the protection of nitrogen, 100mL of trimethylaluminum toluene solution (10 wt%) is added into the reaction kettle, and the temperature of the reaction kettle is controlled to be 0 ℃. A certain amount of distilled deionized water is filled in the branch pipe to lead [ H ] to2O]/[Al]The molar ratio was 0.7, nitrogen was passed through the other end of the branch, and the temperature of the reaction water in the branch was controlled to 5 ℃.
When the reaction is started, the mechanical stirring in the kettle is 500rpm, and the emulsification pump is operated at the rotation speed of 20000rpm, so that the trimethylaluminum solution circulates on the reaction kettle and the external pipeline. First, a quantity of phenol is slowly added to pre-react therewith, [ -OH [ ]]/[AlMe3]The molar ratio is 0.1 and the reaction time is 0.5 h. And then, the reaction water slowly passes through the micro-sieve hole array to enter the main pipeline for reaction by adjusting the micro-positive pressure of the nitrogen. After the reaction water is completely input into the reaction kettle, slowly raising the temperature to 30 ℃, and continuously stirring for reaction for 1 hour.
After the reaction is finished, the discharged reaction liquid is filtered by a sand core funnel and then subjected to pressure reduction to remove toluene, so that a modified methylaluminoxane product is obtained, and the yield is 72%.
Example 6
This example differs from example 5 in that: and a sand core is arranged at the joint of the end of the branch pipe and the main pipeline, and the aperture of the sand core is 2-4 mu m.
The other reaction procedures, conditions and apparatus parameters were the same as those in example 5. The yield of modified methylaluminoxane obtained after the reaction was finished was 76%.
Example 7
This example differs from example 5 in that: and a graphene film is arranged at the joint of the pipe end of the branch pipe and the main pipeline, and the average interlayer spacing of the graphene is 0.4 nm.
The other reaction procedures, conditions and apparatus parameters were the same as those in example 5. The yield of modified methylaluminoxane obtained after the reaction is finished is 80 percent.
Example 8
This example differs from example 7 in that: the initially charged trimethylaluminum toluene solution had a concentration of 20% by weight.
The other reaction procedures, conditions and apparatus parameters were the same as those in example 7. The yield of modified methylaluminoxane obtained after the reaction is finished is 82 percent.
Example 9
This example differs from example 7 in that: the initially charged trimethylaluminum toluene solution had a concentration of 30 wt.%.
The other reaction procedures, conditions and apparatus parameters were the same as those in example 7. The yield of modified methylaluminoxane obtained after the reaction is finished is 81 percent.
Example 10
This example differs from example 7 in that: the amount of phenol added during the pre-reaction is such that [ -OH [)]/[AlMe3]The molar ratio was 0.2.
The other reaction procedures, conditions and apparatus parameters were the same as those in example 7. The yield of modified methylaluminoxane obtained after the reaction is finished is 82 percent.
Example 11
This example differs from example 7 in that: the amount of phenol added during the pre-reaction is such that [ -OH [)]/[AlMe3]The molar ratio was 0.3.
The other reaction procedures, conditions and apparatus parameters were the same as those in example 7. The yield of modified methylaluminoxane obtained after the reaction was completed was 83%.
Example 12
This example differs from example 7 in that: the phenolic compound added in the pre-reaction is 4-methyl-2, 6-di-tert-butylphenol, and the dosage of the phenolic compound meets [ -OH]/[AlMe3]The molar ratio was 0.1.
The other reaction procedures, conditions and apparatus parameters were the same as those in example 7. The yield of modified methylaluminoxane obtained after the reaction is finished is 79 percent.
Example 13
This example differs from example 7 in that: the phenolic compound added in the pre-reaction is 4-methyl-2, 6-di-tert-butylphenol, and the dosage of the phenolic compound meets [ -OH]/[AlMe3]The molar ratio was 0.2.
The other reaction procedures, conditions and apparatus parameters were the same as those in example 7. The yield of modified methylaluminoxane obtained after the reaction is finished is 80 percent.
Example 14
This example differs from example 7 in that: the phenolic compound added in the pre-reaction is 4-methyl-2, 6-di-tert-butylphenolIn an amount satisfying [ -OH [ ]]/[AlMe3]The molar ratio was 0.3.
The other reaction procedures, conditions and apparatus parameters were the same as those in example 7. The yield of modified methylaluminoxane obtained after the reaction is finished is 80 percent.
Example 15
This example differs from example 7 in that: the phenolic compound added in the pre-reaction is 2,3,4,5, 6-pentafluorophenol, and the dosage of the phenolic compound meets [ -OH]/[AlMe3]The molar ratio was 0.1.
The other reaction procedures, conditions and apparatus parameters were the same as those in example 7. The yield of modified methylaluminoxane obtained after the reaction was over was 78%.
Example 16
This example differs from example 7 in that: the phenolic compound added in the pre-reaction is 2,3,4,5, 6-pentafluorophenol, and the dosage of the phenolic compound meets [ -OH]/[AlMe3]The molar ratio was 0.2.
The other reaction procedures, conditions and apparatus parameters were the same as those in example 7. The yield of modified methylaluminoxane obtained after the reaction is finished is 81 percent.
Example 17
This example differs from example 7 in that: the phenolic compound added in the pre-reaction is 2,3,4,5, 6-pentafluorophenol, and the dosage of the phenolic compound meets [ -OH]/[AlMe3]The molar ratio was 0.3.
The other reaction procedures, conditions and apparatus parameters were the same as those in example 7. The yield of modified methylaluminoxane obtained after the reaction is finished is 79 percent.
The modified methylaluminoxane synthesized by the embodiment of the invention is used as a cocatalyst for ethylene polymerization experiment evaluation. As a comparative example, an ethylene polymerization experiment was carried out under the same conditions using methylaluminoxane product (10 wt% toluene solution) produced by Yabao corporation, USA, as a cocatalyst. The results are shown in Table 1.
The main catalyst adopted by the evaluation of polymerization experiments is a catalytic system consisting of a pyridine diimine ligand {2, 6-bis- [ (2-methylanilinoethyl) pyridine ] } and ferric acetylacetonate, and the structure is as follows, and the pyridine diimine ligand {2, 6-bis- [ (2-methylanilinoethyl) pyridine ] } and the ferric acetylacetonate are dissolved in toluene to form a homogeneous catalyst.
A250 mL polymerization reactor was heated to 90 ℃ or higher, vacuum-baked for 2 hours, and replaced with high-purity nitrogen gas several times. The temperature of the reactor was then adjusted to 50 ℃ by circulation of jacketed cooling water, and 50mL of toluene was added as the reaction medium. The concentration of the iron-based main catalyst in the reaction medium was set to 4X 10-5mol/L of [ Al ]]:[Fe]Adding a certain amount of cocatalyst methylaluminoxane according to the molar ratio of 1000, opening an ethylene pressure regulating valve, quickly introducing ethylene and ensuring that the reaction pressure is 0.1MPa, and the reaction time is 30 min. After gas-liquid-solid separation of the product obtained by the reaction, drying and weighing the solid-phase product; the liquid phase product was quantitatively analyzed by gas chromatography. The activity was calculated from the total product yield.
TABLE 1 cocatalyst catalytic Activity comparison
The embodiment shows that the modified alkylaluminoxane preparation method adopted by the invention has high yield, the whole preparation process is safe and controllable by pre-modifying the alkylaluminium and highly dispersing the reaction water, and potential safety hazards such as excessive hydrolysis of the alkylaluminium do not exist. The catalytic activity of the obtained modified alkyl aluminoxane is obviously higher than that of a commercial product under the same conditions.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A process for preparing a modified alkylaluminoxane comprising the steps of:
step S1, pre-reacting alkyl aluminum with a phenolic compound to obtain an aryloxy-modified alkyl aluminum compound;
step S2, thinning and dispersing the reaction water to below 10 microns through a dispersion and release device;
and step S3, controlling the release process of the dispersed reaction water, inputting the reaction water into a reaction system to contact and react with the aryloxy alkylaluminum solution to obtain the aryloxy modified alkylaluminoxane solution.
2. The method of claim 1, wherein in step S1, the aluminum alkyl has the formula AlRnX3-nWherein, R is alkyl, X is one or more selected from aryl, alkoxy and halogen, and n is 1-3.
3. The method according to claim 1, wherein in step S1, the phenolic compound is selected from one or more of phenol, mono-or poly-hydrocarbyl-substituted phenol, mono-or poly-halogen-substituted phenol, mono-or poly-nitrophenol, polyhydric phenol, biphenol, and phenolic hydroxyl group-containing aromatic compounds containing a plurality of different types of substituents, and the amount ratio of the phenolic compound to the aluminum alkyl substance is 0.01 to 1.0 in terms of the ratio of the number of phenolic hydroxyl groups to the number of aluminum atoms.
4. The method of claim 1, wherein in step S2, the water is selected from liquid water, water vapor, an emulsion of water and an inert solvent, a solution of water and a polar solvent, and a mixture of water vapor and an inert gas.
5. The method according to claim 1, wherein in step S2, the reaction water dispersion releaser is a micro-mesh array, a capillary or capillary array, a membrane material, and the pore size of the micro-mesh, the inner diameter of the capillary or the inner diameter of the transmission channel of the membrane material is not more than 10 μm.
6. The method according to claim 1, wherein in step S2, the reaction water dispersion releasing device is selected from a membrane material, the membrane material is an organic, inorganic or organic/inorganic composite membrane material, and the inner diameter of the transmission channel of the membrane material is not more than 100 nm.
7. The method as claimed in claim 1, wherein in step S3, the finely dispersed reaction water is fed into a reactor containing an aryloxyalkyl aluminum solution or a reaction line on which the aryloxyalkyl aluminum solution is mainly fed for contact reaction to obtain an aryloxy-modified alkylaluminoxane solution, wherein the ratio of the amount of the water to the amount of the aryloxyalkyl aluminum species is 0.1 to 1.0.
8. The method according to claim 1, wherein in step S3, the concentration of the aryloxyalkyl aluminum by mass in the solution of the aryloxyalkyl aluminum at the beginning of the reaction is 1 to 40%, and the solution of the aryloxyalkyl aluminum is a solution of the aryloxyalkyl aluminum and an inert reaction medium.
9. The method according to any one of claims 1 to 8, wherein the pre-reaction temperature in step S1 is-20 to 30 ℃, the contact reaction temperature in step S3 is-30 to 50 ℃, and the reaction process can be a constant temperature reaction or a step temperature change reaction.
10. The process of any one of claims 1 to 9, further comprising a step S4 of filtering the aryloxy-modified alkylaluminoxane solution and concentrating to remove part or all of the solvent to obtain a concentrated aryloxy-modified alkylaluminoxane solution or a corresponding solid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910963144.XA CN112645972B (en) | 2019-10-11 | 2019-10-11 | Method for preparing modified alkylaluminoxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910963144.XA CN112645972B (en) | 2019-10-11 | 2019-10-11 | Method for preparing modified alkylaluminoxane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112645972A true CN112645972A (en) | 2021-04-13 |
| CN112645972B CN112645972B (en) | 2023-11-21 |
Family
ID=75343375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910963144.XA Active CN112645972B (en) | 2019-10-11 | 2019-10-11 | Method for preparing modified alkylaluminoxane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112645972B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033810A (en) * | 1987-11-23 | 1989-07-12 | 联合碳化公司 | The preparation method of aikyiaiurnirsoxan beta |
| US5599964A (en) * | 1996-04-19 | 1997-02-04 | Albemarle Corporation | Continuous process for preparing hydrocarbylaluminoxanes |
| US5728855A (en) * | 1995-10-19 | 1998-03-17 | Akzo Nobel Nv | Modified polyalkylaluminoxane composition formed using reagent containing carbon-oxygen double bond |
| US6153550A (en) * | 1997-12-18 | 2000-11-28 | Mobile Oil Corporation | Olefin polymerization catalyst based on metallocene complexes and perfluorinated oligoaryl derivatives of aluminates |
| CN102190677A (en) * | 2010-03-03 | 2011-09-21 | 中国石油天然气股份有限公司 | Atomization synthesizer and application thereof in synthesis of alkylaluminoxane |
| RU2014128059A (en) * | 2014-07-10 | 2016-02-10 | Федеральное государственное бюджетное учреждение науки Институт проблем химической физики Российской академии наук (ИПХФ РАН) | The use of alkylaluminum aryloxides as activators of metallocene catalysts for the homo- and copolymerization of olefins and dienes, homogeneous metallocene catalyst systems for the synthesis of homo- and copolymers of olefins and dienes, a method for producing homo- and copolymers of olefins and dienes, a method for stabilizing homo- and copolymers of olefins and dienes |
| US20190345273A1 (en) * | 2016-05-06 | 2019-11-14 | Scg Chemicals Co., Ltd. | Catalytic support and uses thereof |
-
2019
- 2019-10-11 CN CN201910963144.XA patent/CN112645972B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033810A (en) * | 1987-11-23 | 1989-07-12 | 联合碳化公司 | The preparation method of aikyiaiurnirsoxan beta |
| US5728855A (en) * | 1995-10-19 | 1998-03-17 | Akzo Nobel Nv | Modified polyalkylaluminoxane composition formed using reagent containing carbon-oxygen double bond |
| US5599964A (en) * | 1996-04-19 | 1997-02-04 | Albemarle Corporation | Continuous process for preparing hydrocarbylaluminoxanes |
| US6153550A (en) * | 1997-12-18 | 2000-11-28 | Mobile Oil Corporation | Olefin polymerization catalyst based on metallocene complexes and perfluorinated oligoaryl derivatives of aluminates |
| CN102190677A (en) * | 2010-03-03 | 2011-09-21 | 中国石油天然气股份有限公司 | Atomization synthesizer and application thereof in synthesis of alkylaluminoxane |
| RU2014128059A (en) * | 2014-07-10 | 2016-02-10 | Федеральное государственное бюджетное учреждение науки Институт проблем химической физики Российской академии наук (ИПХФ РАН) | The use of alkylaluminum aryloxides as activators of metallocene catalysts for the homo- and copolymerization of olefins and dienes, homogeneous metallocene catalyst systems for the synthesis of homo- and copolymers of olefins and dienes, a method for producing homo- and copolymers of olefins and dienes, a method for stabilizing homo- and copolymers of olefins and dienes |
| US20190345273A1 (en) * | 2016-05-06 | 2019-11-14 | Scg Chemicals Co., Ltd. | Catalytic support and uses thereof |
Non-Patent Citations (1)
| Title |
|---|
| 丁秀瓶: "甲基铝氧烷的研究与开发进展", 《现代化工》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112645972B (en) | 2023-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW482771B (en) | Preparation of low molecular weight, highly reactive polyisobutylene | |
| CN111647012A (en) | Method for preparing alkylaluminoxane by using microreactor | |
| CN103087221B (en) | Polymer hydrogenation method | |
| CN100390206C (en) | Catalyst active constituent and catalyst containing same | |
| CN111960964A (en) | Fluorine substituted alpha-diimine ligand, nickel catalyst, preparation method and application thereof | |
| CN112645974B (en) | Controllable preparation method of alkyl aluminoxane | |
| CN111004265A (en) | Method for preparing alkyl aluminoxane | |
| CN112645972A (en) | Method for preparing modified alkylaluminoxane | |
| CN112645973B (en) | Controllable preparation method of modified alkylaluminoxane | |
| CN100537614C (en) | Method for synthesizing in situ polyethylene catalyst of non - metallocene in load type | |
| CN114870901B (en) | Bisphosphite polymer catalyst for olefin hydroformylation, preparation method and application thereof | |
| CN102190678B (en) | Method for preparing modification aluminoxane | |
| CN102040685B (en) | Catalyst component for ethylene polymerization and catalyst | |
| WO2023152332A1 (en) | Method for the production of organometallic compounds | |
| CN108084305B (en) | Ethylene polymerization solid titanium catalyst component, preparation method thereof and ethylene polymerization solid titanium catalyst | |
| CN112375095B (en) | Continuous process for preparing methylaluminoxane | |
| CN101255204B (en) | Method for preparing supported non-metallocene olefin polymerization catalyst | |
| US11712675B2 (en) | Molecular sieve-based catalyst modification apparatus, and method | |
| CN113024724B (en) | Method for continuous polymerization of cracked fractions | |
| CN113559924A (en) | Ionic liquid catalyst and preparation method and application thereof | |
| CN103073660B (en) | Magnesium halide carrier and application thereof, and olefin polymerization catalyst, olefin polymerization catalyst system, and olefin polymerization method | |
| JP4544659B2 (en) | Method for producing aluminoxane | |
| CN115121200B (en) | Method for continuously preparing alkylaluminoxane based on micro-membrane reactor | |
| CN117820522B (en) | Olefin polymerization catalyst, preparation method and application | |
| CN115838448B (en) | Supported catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |