CN112645972B - Method for preparing modified alkylaluminoxane - Google Patents
Method for preparing modified alkylaluminoxane Download PDFInfo
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- CN112645972B CN112645972B CN201910963144.XA CN201910963144A CN112645972B CN 112645972 B CN112645972 B CN 112645972B CN 201910963144 A CN201910963144 A CN 201910963144A CN 112645972 B CN112645972 B CN 112645972B
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 141
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 32
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 25
- 150000002989 phenols Chemical class 0.000 claims abstract description 24
- -1 aryloxy modified alkyl aluminum compound Chemical class 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 13
- 125000005160 aryl oxy alkyl group Chemical group 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000007670 refining Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 16
- 125000004104 aryloxy group Chemical group 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
- 239000000839 emulsion Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 150000008442 polyphenolic compounds Polymers 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
- 238000001914 filtration Methods 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
- 230000000977 initiatory effect Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 17
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 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 17
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 230000007062 hydrolysis Effects 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 230000036571 hydration Effects 0.000 description 8
- 238000006703 hydration reaction Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 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
- 230000003197 catalytic effect Effects 0.000 description 6
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 6
- 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
- 238000010438 heat treatment Methods 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
- 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 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012295 chemical reaction liquid Substances 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
- 238000002474 experimental method Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000002994 raw material Substances 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
- 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
- 239000004411 aluminium Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 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
- 238000004821 distillation Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010024769 Local reaction Diseases 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 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
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation 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
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002815 homogeneous catalyst Substances 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
- 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
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000002156 mixing Methods 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
- 229910001848 post-transition metal Inorganic materials 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
- 238000006467 substitution reaction Methods 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
- 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
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Toxicology (AREA)
Abstract
The invention discloses a method for preparing modified alkyl aluminoxane, which comprises the following steps: step S1, pre-reacting alkyl aluminum with a phenolic compound to obtain an aryloxy modified alkyl aluminum compound; s2, refining and dispersing the reaction water to be less than 10 microns through a dispersion and release device; and S3, controlling the release process of the dispersed reaction water, and inputting the reaction water into a reaction system to contact and react with an aryloxy alkyl aluminum solution to obtain an aryloxy modified alkyl aluminum oxide 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, ensures safe and controllable production process, greatly reduces the possibility of excessive hydrolysis reaction, and has higher activity and stability.
Description
Technical Field
The invention relates to preparation of polyolefin cocatalysts, in particular to a method for preparing modified alkylaluminoxane.
Background
Alkyl aluminoxane is an important cocatalyst of polyolefin catalyst, and can be combined with metallocene catalyst or post-transition metal catalyst to catalyze olefin polymerization or copolymerization to produce a series of high-end polyolefin materials with accurately adjustable microstructure and excellent performance, which plays a vital role in the development of polyolefin industry.
The alkyl aluminoxane can be mainly prepared by partial hydrolysis of alkyl aluminum, and as the alkyl aluminum is very active and reacts with water vigorously, how to effectively control the reaction process becomes the research focus of the preparation process. The existing researches are mainly focused on the aspects of introducing the reaction water, improving the preparation process and the like, and the preparation method can be divided into two major categories of hydrolysis method and non-hydrolysis method according to the aspects.
The hydrolysis method is characterized in that alkyl aluminum is reacted with water to generate alkyl aluminoxane, and the alkyl aluminoxane can be divided into an indirect hydration method and a direct hydration method according to the state of water used in the reaction. The indirect hydration method mainly adopts inorganic salt containing crystal water or porous substance absorbing water to react with alkyl aluminum, and the common crystal hydrate comprises CuSO 4 ·5H 2 O、FeSO 4 ·7H 2 O、Al 2 (SO 4 ) 3 ·18H 2 O、LiBr·2H 2 O, etc. The main problems of the process are that the surface of inorganic salt serving as a carrier of water can adsorb a part of generated aluminoxane products, the separation is difficult to effectively separate, 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. Because the direct reaction of the two is very intense, when the direct hydration method is adopted, special designs are often needed for reaction equipment, and the special designs have high requirements for reaction control and synthesis devices. However, the direct hydration method is higher than the indirect hydration method in terms of the product yield.
In order to avoid severe hydrolysis reactions, researchers at Akzo Nobel have developed non-hydrolytic processes by reacting an aluminum alkyl with a carbon-oxygen bond-containing compound (e.g., CO 2 Benzoic acid, etc.) to form a primary product, which is subsequently converted to aluminoxane by heating or catalytic methods, 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 products are not applicable to all single-site catalytic systems, so that the method cannot directly replace hydrolyzed alkyl aluminoxane in industrial production.
In general, the direct hydration process is currently the most suitable process for the large-scale production of the most versatile and efficient alkylaluminoxane. However, from the perspective of improving the safety of the production process and the yield of the product, a key technical difficulty to be solved at present is how to realize the high dispersion of water, and the consequences of excessive local reaction or incomplete reaction caused by uneven concentration distribution of water in the reaction process, such as affected composition and performance of the target product, are prevented.
On the other hand, it is also possible to achieve effective control of the hydrolysis process by reducing the reactivity of the aluminum alkyls. The substitution of partial alkyl with lower activity can reduce the activity of alkyl aluminum and the hydrolysis rate effectively, so that the hydrolysis process is milder and controllable, and the introduction of proper groups can regulate the structure and Lewis acidity of alkyl aluminoxane product and raise its catalytic activity and stability. Accordingly, the development of corresponding modified alkylaluminoxane is attracting attention and importance from the viewpoint of modification of alkylaluminum.
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 with 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 one aspect of the present invention, there is provided 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;
s2, refining and dispersing the reaction water to be less than 10 microns through a dispersion and release device;
and S3, controlling the release process of the dispersed reaction water, and inputting the reaction water into a reaction system to contact and react with an aryloxy alkyl aluminum solution to obtain an aryloxy modified alkyl aluminum oxide solution.
In step S1 of the present invention, the aluminum alkyl has the formula AlR n X 3-n Wherein R is alkyl, and X is selected from one or more of aryl, alkoxy and halogen，n＝1-3。
According to a preferred embodiment of the present invention, the aluminum alkyl is a trialkylaluminum of the formula AlR 3 Wherein R is C 1 -C 10 Alkyl of (a); preferably, R is C 1 -C 4 An 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 polyhydrocarbyl substituted phenol, mono-or polyhalo substituted phenol, mono-or polynitrophenol, polyhydroxy 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 poly-alkyl substituted phenol, mono-or poly-phenyl substituted phenol, mono-or poly-halogen substituted phenol, phenol containing alkyl and halogen substituents, phenol containing phenyl and halogen substituents, biphenol and polyhydroxy 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 substance of the aluminum alkyl is 0.01 to 1.0, preferably 0.1 to 1.0, 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 the step S1 of the invention, the phenolic compound can cause partial alkyl groups to be substituted by corresponding aryloxy groups through the reaction of active hydrogen on phenolic hydroxyl groups and alkyl groups in aluminum alkyl. In the hydrolysis reaction, the reactivity of aryloxy is obviously weaker than that of alkyl, so that the reactivity of aluminum alkyl can be reduced by the pre-modification strategy, and the reaction with water can be more gently controlled. The above-mentioned ratio of the amount of the phenolic compound to the amount of the aluminum alkyl can be within a range that satisfies the requirement that after a portion of the alkyl groups are substituted, the remaining alkyl groups still participate in the further hydrolysis reaction sufficiently to give the appropriate aluminoxane structure. In addition, the aryloxy group introduced has the same hetero atom as that of the aluminoxane, i.e., an oxygen atom, and thus has good compatibility with the aluminoxane structure. In the hydrolysis reaction, oxygen in the aryloxy group can participate in the construction of an aluminoxane structural unit such as Al-O-Al, and the like, so that the aryloxy aluminoxane with high stability is formed, and the aryloxy group is tightly combined 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 by a nano/micron or even molecular dispersion releasing device, wherein the core component of the dispersion releasing 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 aperture of the micro-sieve pore, the inner diameter of the capillary or the inner diameter of a transmission channel of the membrane material is not more than 10 mu m, preferably not more than 1 mu m.
According to a preferred embodiment of the present invention, in step S2, the molecular-level 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, more preferably not more than 2nm. Specifically, the membrane material is an organic, inorganic or organic/inorganic composite membrane material, for example, an advanced membrane material with an inner diameter ranging from Emi to a nanoscale pore canal 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 releasing device.
According to a preferred embodiment of the present invention, the reaction water dispersion and release device further comprises a support assembly, a fixing assembly and the like for the core assembly, in addition to the core assembly.
According to a preferred embodiment of the present invention, the reaction water may be dispersed by the dispersion releasing means under pressure.
In the step S3 of the invention, the control of the release process of the reaction water dispersion is realized by controlling the conditions of the reaction water form, the transmission temperature, the transmission pressure (driving force), the number and the size of transmission channels, the thickness of a film material or the area of the film material, and the like, and then the reaction water subjected to the refining dispersion is input into a kettle type reactor containing an aryloxy alkyl aluminum solution or a tubular/annular pipe type continuous flow reactor taking the aryloxy alkyl aluminum solution as a main fluid for contact reaction, so that the aryloxy modified alkyl aluminum alkyl solution is obtained.
According to a preferred embodiment of the present invention, the reactor may be externally applied with one or more of an ultra-gravitational field, an ultrasonic field, an electric field or a magnetic field, or may be a combination of multiple reactors in series and/or parallel, and the reaction water dispersion releasing device may 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, capillary or capillary array, membrane material, etc. are directly contacted with the aryloxyalkyl aluminum solution or the main fluid of the aryloxyalkyl aluminum solution at one side of the reaction system to facilitate the mixing of the reaction water directly into the reaction system after passing through the transmission channel, more preferably, an ultrasonic dispersing device or a mechanical emulsifying device may be added on the tank reactor or the reaction tube near the reaction water input, thereby facilitating the further dispersion of the reaction water in the reaction system.
According to a preferred embodiment of the invention, step S3 is carried out with an initial solution of aryloxyalkyl aluminium having a mass concentration of from 1 to 40%, preferably from 1 to 20%.
According to a preferred embodiment of the present invention, the aryloxyalkyl aluminum solution is a solution of 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 C 6 -C 10 Aromatic hydrocarbons, preferably one or more selected from benzene, toluene, xylene and ethylbenzene.
In a preferred embodiment of the present invention, the inert reaction medium is toluene.
According to a preferred embodiment of the invention, the ratio of the amount of water to the amount of the substance of the aryloxyalkyl aluminium 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 temperature of the pre-reaction 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 performed by a constant temperature reaction or a stepwise variable temperature reaction.
According to a preferred embodiment of the invention, the process further comprises 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 corresponding solid, wherein the concentrating is performed by evaporation in a reduced pressure distillation or evaporator, preferably the temperature of the reduced pressure distillation or evaporator is not higher than 60 ℃.
The beneficial effects are that:
the method for preparing the modified alkyl aluminoxane is simple and feasible and is flexible to operate. Firstly, a phenolic compound is adopted to modify the raw material aluminum alkyl, so that the reactivity and the subsequent reaction rate when the raw material aluminum alkyl contacts water are effectively reduced; and secondly, through the high dispersion of water, the mass transfer and diffusion of the water in the reaction solution can be greatly promoted, the contact reaction efficiency is remarkably improved, and the occurrence of the conditions of excessive hydrolysis and the like caused by the uneven local concentration of the water is effectively reduced.
The invention starts from two raw materials in the reaction process, so that the hydrolysis reaction process is safer and more controllable, and the product yield is high. Meanwhile, the modified alkyl aluminoxane has better stability, and the existence of aryloxy can prevent interaction and condensation among alkyl aluminoxane molecules, so as to avoid gel precipitation caused by further increase of molecular weight.
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 formed in the side wall of the 250mL reaction kettle and is connected with a section of stainless steel pipe which is inclined upwards at 45 degrees with the kettle body, a stainless steel sheet with micro-sieve holes uniformly distributed is arranged at the orifice, and the aperture of the micro-sieve holes is 10 mu m. The reaction kettle is provided with a nitrogen inlet, a vent valve and a cooling jacket, and is added with the nitrogen under the protection of nitrogen100mL of trimethylaluminum toluene solution (10 wt%) was added, and the reaction vessel temperature was controlled to 0 ℃. Filling a certain amount of distilled deionized water into a stainless steel tube to ensure that [ H ] 2 O]/[Al]The molar ratio is 0.7, the other end of the steel tube is filled with nitrogen, and the temperature of the reaction water in the stainless steel tube is controlled to be 5 ℃.
When the reaction is started, firstly, the trimethylaluminum solution is stirred at a rotation speed of 500rpm, and a certain amount of phenol is slowly added to react with the trimethylaluminum solution in advance, [ -OH]/[AlMe 3 ]The molar ratio was 0.1 and the reaction time was 0.5h.
After the pre-reaction is finished, the reaction water slowly enters the reaction kettle through the micro-sieve pore array to contact and react by adjusting the micro-positive pressure of nitrogen. After the reaction water is completely input into the reaction kettle, slowly heating to 30 ℃, and continuously stirring and reacting for 1h.
After the reaction is finished, the discharged reaction liquid is filtered by a sand core funnel, and then toluene is removed under reduced pressure, so that a modified methylaluminoxane product is obtained, and the yield is 67%.
Example 2
This embodiment differs from embodiment 1 in that: the orifice is embedded into a sand core, and the aperture of the sand core is 2-4 mu m.
Other reaction processes, conditions and apparatus parameters were the same as in example 1. The reaction was completed to give a modified methylaluminoxane yield of 69%.
Example 3
A stainless steel pipe with an inner diameter of 1cm is inserted from the top of a 250mL reaction kettle, the pipe end is close to the upper part of a stirring paddle, a screen mesh is fixed at the pipe end and used as a supporting body, a molecular sieve membrane is arranged on the screen mesh in the pipe, and the average pore diameter is 0.5nm. The reaction kettle is provided with a nitrogen inlet, a vent 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 ℃. Filling a certain amount of distilled deionized water into a stainless steel tube to ensure that [ H ] 2 O]/[Al]The molar ratio is 0.7, and the other end of the steel tube is filled with nitrogen.
When the reaction is started, firstly, the trimethylaluminum solution is stirred at a rotation speed of 500rpm, and a certain amount of phenol is slowly added to react with the trimethylaluminum solution in advance, [ -OH]/[AlMe 3 ]The molar ratio was 0.1 and the reaction time was 0.5h.
After the pre-reaction is finished, the reaction water slowly passes through the molecular sieve membrane to enter the reaction kettle for contact reaction by adjusting the micro positive pressure of nitrogen. After the reaction water is completely input into the reaction kettle, slowly heating to 30 ℃, and continuously stirring and reacting for 1h.
After the reaction is finished, the discharged reaction liquid is filtered by a sand core funnel, and then toluene is removed under reduced pressure, so that a modified methylaluminoxane product is obtained, and the yield is 74%.
Example 4
This embodiment differs from embodiment 3 in that: and a graphene film is arranged on the screen in the pipe, and the average interlayer spacing of the graphene is 0.4nm.
Other reaction processes, conditions and apparatus parameters were the same as in example 3. The reaction was completed to give a modified methylaluminoxane yield of 75%.
Example 5
And a pipeline led out from the bottom of the 250mL reaction kettle is connected with an online emulsion pump, and the pump outlet pipeline returns to the reaction kettle from the top of the kettle to form material external circulation. And a branch pipe is arranged on a pipeline near the inlet of the emulsion pump, a stainless steel sheet with micro-sieve pores uniformly distributed is arranged at the joint of the pipe end of the branch pipe and the main pipeline, and the diameter of the micro-sieve pores is 10 mu m. The reaction kettle is provided with a nitrogen inlet, a vent 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 ℃. Adding distilled deionized water into branch pipe to make [ H ] 2 O]/[Al]The molar ratio is 0.7, the other end of the branch pipe is filled with nitrogen, and the temperature of the reaction water in the branch pipe is controlled to be 5 ℃.
When the reaction is started, the mechanical stirring in the reactor is 500rpm, and meanwhile, the emulsifying pump is operated at the rotating speed of 20000rpm, so that the trimethylaluminum solution circulates on the reaction reactor and an external pipeline. Firstly, slowly adding a certain amount of phenol to react with the phenol in advance, [ -OH]/[AlMe 3 ]The molar ratio was 0.1 and the reaction time was 0.5h. Subsequently, the reaction water was slowly passed through the array of micromesh holes into the main line for reaction by adjusting the micro positive pressure of nitrogen. After the reaction water is completely input into the reaction kettle, slowly heating to 30 ℃, and continuously stirring and reacting for 1h.
After the reaction is finished, the discharged reaction liquid is filtered by a sand core funnel, and then toluene is removed under reduced pressure, so that a modified methylaluminoxane product is obtained, and the yield is 72%.
Example 6
This embodiment differs from embodiment 5 in that: and a sand core is arranged at the joint of the pipe ends of the branch pipes and the main pipeline, and the aperture of the sand core is 2-4 mu m.
Other reaction processes, conditions and apparatus parameters were the same as in example 5. The reaction was completed to give a modified methylaluminoxane yield of 76%.
Example 7
This embodiment differs from embodiment 5 in that: and a graphene film is arranged at the joint of the pipe ends of the branch pipes and the main pipeline, and the average interlayer spacing of the graphene is 0.4nm.
Other reaction processes, conditions and apparatus parameters were the same as in example 5. The reaction was completed to give a modified methylaluminoxane yield of 80%.
Example 8
This embodiment differs from embodiment 7 in that: the concentration of the initially charged trimethylaluminum toluene solution was 20wt%.
Other reaction processes, conditions and apparatus parameters were the same as in example 7. The reaction was completed to give a modified methylaluminoxane yield of 82%.
Example 9
This embodiment differs from embodiment 7 in that: the concentration of the initially charged trimethylaluminum toluene solution was 30wt%.
Other reaction processes, conditions and apparatus parameters were the same as in example 7. The reaction was completed to give a modified methylaluminoxane yield of 81%.
Example 10
This embodiment differs from embodiment 7 in that: the amount of phenol added during the pre-reaction satisfies [ -OH]/[AlMe 3 ]The molar ratio was 0.2.
Other reaction processes, conditions and apparatus parameters were the same as in example 7. The reaction was completed to give a modified methylaluminoxane yield of 82%.
Example 11
This embodiment differs from embodiment 7 in that: the amount of phenol added during the pre-reaction satisfies [ -OH]/[AlMe 3 ]The molar ratio was 0.3.
Other reaction processes, conditions and apparatus parameters were the same as in example 7. The reaction was completed to give a modified methylaluminoxane yield of 83%.
Example 12
This embodiment differs from embodiment 7 in that: the phenolic compound added in the pre-reaction is 4-methyl-2, 6-di-tert-butylphenol, and the dosage satisfies [ -OH]/[AlMe 3 ]The molar ratio was 0.1.
Other reaction processes, conditions and apparatus parameters were the same as in example 7. The reaction was completed to give a modified methylaluminoxane yield of 79%.
Example 13
This embodiment differs from embodiment 7 in that: the phenolic compound added in the pre-reaction is 4-methyl-2, 6-di-tert-butylphenol, and the dosage satisfies [ -OH]/[AlMe 3 ]The molar ratio was 0.2.
Other reaction processes, conditions and apparatus parameters were the same as in example 7. The reaction was completed to give a modified methylaluminoxane yield of 80%.
Example 14
This embodiment differs from embodiment 7 in that: the phenolic compound added in the pre-reaction is 4-methyl-2, 6-di-tert-butylphenol, and the dosage satisfies [ -OH]/[AlMe 3 ]The molar ratio was 0.3.
Other reaction processes, conditions and apparatus parameters were the same as in example 7. The reaction was completed to give a modified methylaluminoxane yield of 80%.
Example 15
This embodiment differs from embodiment 7 in that: the phenolic compound added in the pre-reaction is 2,3,4,5, 6-pentafluorophenol, and the dosage satisfies [ -OH]/[AlMe 3 ]The molar ratio was 0.1.
Other reaction processes, conditions and apparatus parameters were the same as in example 7. The reaction was completed to give a modified methylaluminoxane yield of 78%.
Example 16
This embodiment differs from embodiment 7 in that: the phenolic compound added in the pre-reaction is 2,3,4,5, 6-pentafluorophenol, and the dosage satisfies [ -OH]/[AlMe 3 ]The molar ratio was 0.2.
Other reaction processes, conditions and apparatus parameters were the same as in example 7. The reaction was completed to give a modified methylaluminoxane yield of 81%.
Example 17
This embodiment differs from embodiment 7 in that: the phenolic compound added in the pre-reaction is 2,3,4,5, 6-pentafluorophenol, and the dosage satisfies [ -OH]/[AlMe 3 ]The molar ratio was 0.3.
Other reaction processes, conditions and apparatus parameters were the same as in example 7. The reaction was completed to give a modified methylaluminoxane yield of 79%.
Ethylene polymerization experiments were evaluated using the modified methylaluminoxane synthesized in the examples of the present invention as a cocatalyst. As a comparative example, an ethylene polymerization experiment was performed under the same conditions using a methylaluminoxane product (10 wt% toluene solution) produced by Yabao corporation of America as a cocatalyst. The results are shown in Table 1.
The main catalyst adopted in the polymerization experiment evaluation is a catalytic system composed of pyridine diimine ligand {2, 6-di- [ (2-methylanilino ethyl) pyridine ] } and ferric acetylacetonate, and the structure is as follows, and the pyridine diimine ligand {2, 6-di- [ (2-methylanilino ethyl) pyridine ] } and ferric acetylacetonate are dissolved in toluene to form a homogeneous catalyst.
The 250mL polymerization reactor was heated to above 90℃and baked under vacuum for 2h with multiple displacements with high purity nitrogen. The reaction vessel temperature was then adjusted to 50℃by jacket cooling water circulation and 50mL of toluene was added as the reaction medium. The concentration of the iron-based procatalyst in the reaction medium was set to 4X 10 -5 mol/L of [ Al ]]:[Fe]A certain amount of promoter methylaluminoxane was added in a molar ratio of =1000, the ethylene pressure regulating valve was opened, ethylene was rapidly introduced and the reaction pressure was ensured to be 0.1MPa, and the reaction time was 30min. After gas-liquid-solid separation, the solid-phase product is dried and weighed; the liquid phase product was quantitatively analyzed by gas chromatography. The activity was calculated by total product amount.
TABLE 1 comparison of promoter catalytic Activity
From the above examples, the modified alkyl aluminoxane preparation method adopted in the invention has high yield, and the whole preparation process is safe and controllable by pre-modifying the alkyl aluminum and highly dispersing the reaction water, and has no potential safety hazards such as excessive hydrolysis of the alkyl aluminum. The catalytic activity of the resulting modified alkylaluminoxane under the same conditions is significantly higher than the commercial product level.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (5)
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;
s2, refining and dispersing the reaction water to be less than 10 microns through a dispersion and release device;
s3, controlling the release process of the dispersed reaction water, and inputting the reaction water into a reaction system to contact and react with an aryloxy alkyl aluminum solution to obtain an aryloxy modified alkyl aluminum oxide solution;
step S4, filtering the aryloxy modified alkylaluminoxane solution, concentrating to remove part or all of the solvent to obtain a concentrated aryloxy modified alkylaluminoxane solution or corresponding solid;
in the step S1, the phenolic compound is selected from one or more of phenol, single or multi-alkyl substituted phenol, single or multi-halogen substituted phenol, single or multi-nitrophenol, polyhydroxy phenol, biphenol and aromatic compound containing phenolic hydroxyl groups and containing a plurality of different types of substituents, and the ratio of the quantity of the phenolic compound to the quantity of the substance of alkyl aluminum is 0.01-1.0 in terms of the ratio of the quantity of phenolic hydroxyl groups to the quantity of aluminum atoms;
in the step S2, the reaction water dispersion and release device is a micromesh array, a capillary or a capillary array and a membrane material, wherein the aperture of the micromesh, the inner diameter of the capillary or the inner diameter of a transmission channel of the membrane material is not more than 10 mu m;
in the step S1, the general formula of the aluminum alkyl is AlR n X 3-n Wherein R is alkyl, X is selected from one or more of aryl, alkoxy, and halogen, n=1-3;
in step S2, the reaction 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.
2. The method according to claim 1, wherein in step S2, the reaction water dispersion and release device is made of a membrane material, the membrane material is an organic, inorganic or organic/inorganic composite membrane material, and the inner diameter of a transmission channel of the membrane material is not more than 100 nm.
3. The method according to claim 1, wherein in step S3, finely dispersed reaction water is fed into a reactor containing an aryloxyalkyl aluminum solution or a reaction line containing an aryloxyalkyl aluminum solution as a main fluid for contact reaction to obtain an aryloxyalkyl aluminum modified solution, wherein the ratio of the amount of water to the amount of aryloxyalkyl aluminum is 0.1 to 1.0.
4. The method according to claim 1, wherein in step S3, the concentration of the aryloxyalkyl aluminum in the reaction initiation aryloxyalkyl aluminum solution is 1 to 40% by mass, and the aryloxyalkyl aluminum solution is a solution formed by aryloxyalkyl aluminum and an inert reaction medium.
5. The method according to any one of claims 1 to 4, wherein in the step S1, the pre-reaction temperature is-20 to 30 ℃, and in the step S3, the contact reaction temperature is-30 to 50 ℃, and the reaction process can be a constant temperature reaction or a stepwise variable temperature reaction.
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