CN1045446C - Process for producing low-polymer alumin oxyane - Google Patents
Process for producing low-polymer alumin oxyane Download PDFInfo
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- CN1045446C CN1045446C CN95107483A CN95107483A CN1045446C CN 1045446 C CN1045446 C CN 1045446C CN 95107483 A CN95107483 A CN 95107483A CN 95107483 A CN95107483 A CN 95107483A CN 1045446 C CN1045446 C CN 1045446C
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- water
- inert solvent
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- aluminum alkyls
- emulsion
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Abstract
The present invention provides a process for producing low-polymer alkyl aluminum, which comprises: an emulsifying agent is used for preparing oil pocket water emulsion of water/an inert solvent; then, the oil pocket water emulsion is dripped in inert solvent solution of an organic aluminum compound for a reaction. Low-polymer alkyl aluminum solution or suspension obtained by the reaction does not need further separating and purifying and can be directly used as a cocatalyst of olefinic polymerization, with good common storage stability.
Description
The invention relates to the preparation method of aikyiaiurnirsoxan beta, more particularly, is the preparation method about the oligomeric aikyiaiurnirsoxan beta of the promotor of the metalloscene catalyst that is used for olefinic polymerization.
Aikyiaiurnirsoxan beta generally obtains by the controlled partial hydrolysis of organoaluminum.Because the reactive behavior of organo-aluminium compound high (when trimethyl aluminium, triethyl aluminum react with water even can blast), subtle change in the reaction process brings marked difference just can for the performance of product, so the reaction of organo-aluminium compound and water is difficult to control.
United States Patent (USP) 3,242,099 discloses a kind ofly by preparing the method for alkylaluminoxane in the inert solvent solution that water is added aluminum alkyls, and this method must be carried out at low temperatures and strict control adds water speed to guarantee to generate aikyiaiurnirsoxan beta rather than aluminium hydroxide.
United States Patent (USP) 3,300,458 disclose by inert solvent solution that makes alkyl aluminium and the method that is mixed with alkylaluminoxane with water saturated hydrocarbon solvent (water is contacted in the solvent saturex with solvent).Because the content of water is very little in the hydrocarbon solvent, so this method need be used a large amount of solvents.
Can relax reaction because crystal water is more stable comparatively speaking, people have proposed many methods of utilizing salt hydrate as water source and trialkylaluminium reaction, for example, use CuSO
45H
2The method of O (United States Patent (USP) 4,404,344,4,542,199), use Al
2(SO
4)
39H
2The method of O (United States Patent (USP) 4,544,762) and use FeSO
47H
2The method of O (United States Patent (USP) 4,665,208).These class methods need prevent the pollution of salt, because in olefinic polymerization, residual salt can cause poisoning of catalyst.
United States Patent (USP) 4,730,071 disclose a kind of utilize ultrasonic wave with water-dispersion in inert solvent, then the inert solvent solution of trialkylaluminium is added the method for preparing aikyiaiurnirsoxan beta in the gained dispersion liquid.United States Patent (USP) 4,730,072 similarly, the inert solvent dispersion liquid that just utilize at a high speed, high-shear mixer forms water.
United States Patent (USP) 4,772,736 disclosed methods be water is introduced alkyl aluminium solution liquid level down near the position of agitator so that water is distributed in the solution immediately.
United States Patent (USP) 4,924,018 discloses a kind of continuation method, this method is that the emulsion of the inert solvent solution of aluminum alkyls and water/inert solvent is sent into first reactor, again reaction mixture is moved in second reactor by first reactor, to keep the constant and certain reaction residence time of liquid level in first reactor.Wherein the emulsion of water/inert solvent utilizes static mixer to obtain.
United States Patent (USP) 4,968,827 disclosed methods are that the temperature water being delivered to the gas-phase space of alkyl aluminium solution top and keep reaction mixture is in-80 ℃ to-10 ℃ scope.
Above-mentioned United States Patent (USP) 4,730,071,4,730,072,4,928,018 all needs specific installation, United States Patent (USP) 4,968,827 needs low-temp reactions.In addition, a common drawback of aforesaid method is the restriction that is subjected to the solubleness of water, and shipwreck is to be well dispersed in the inert solvent.
The purpose of this invention is to provide a kind of method that specific installation, high productivity prepare oligomeric aikyiaiurnirsoxan beta that need not.
The preparation method of oligomeric aikyiaiurnirsoxan beta provided by the invention comprises the water-in-oil emulsion for preparing water/inert solvent with emulsifying agent, then it is splashed in the inert solvent solution of organo-aluminium compound to react.
The aikyiaiurnirsoxan beta that adopts this method to synthesize has linear or ring texture, and its chemical formula is as follows:
Wherein, R is C
1-C
6Alkyl, preferred C
1-C
4Alkyl is as methyl, ethyl, isobutyl-etc., particularly methyl; N is 2～40 integer, preferred 10～30 integer.
According to method provided by the invention, oligomeric aikyiaiurnirsoxan beta with linear or ring texture is preparation like this: with emulsifying agent water and inert solvent are made water-in-oil emulsion with known emulsification means, inert solvent wherein: water: the volume ratio of emulsifying agent is 100: 0.5～10: 0.1～1, preferred 100: 1～5: 0.2～0.5; Organo-aluminium compound is dissolved in to make organo-aluminium compound concentration in the inert solvent be 5～30 heavy %, the solution of preferred 10～20 heavy %; In inert atmosphere, stirring down above-mentioned emulsion is 0.8～2: 1 according to the mol ratio of water in organo-aluminium compound and the emulsion, preferred 1～1.5: 1 consumption splashes in the solution of organo-aluminium compound, dropping temperature should be controlled at-10～40 ℃, preferred 0～20 ℃, rate of addition is 0.2～20 ml/min, preferred 0.5～5 ml/min, after dropwising system is warming up to 40～80 ℃, preferred 40～60 ℃ of reactions 1～4 hour.
Emulsifying agent used in the inventive method is for forming the tensio-active agent of water-in-oil emulsion, and its hydrophile-lipophile balance value (HLB) is advisable with 2～6, and preferred 3～5.The example of the emulsifying agent that is suitable for has polyalcohols nonionogenic tenside, polyoxyethylene nonionogenic tenside.Such tensio-active agent can generate the aluminum alkoxide compounds with the organo-aluminium compound reaction, and does not influence the use of the oligomeric aikyiaiurnirsoxan beta of purpose product in olefinic polymerization.
Water as reaction raw materials can be ortho-water, but preferably uses distilled water or deionized water.
Known emulsification means are meant the various means that can form uniform finely divided emulsion usually, comprise simple agitation, high-speed stirring, colloidal mill grinding, homogenizer homogeneous, supersonic method etc.
The inert solvent that is used for disperse water or is dissolved with machine aluminium compound can be the same or different, they can be saturated alkane, naphthenic hydrocarbon, aromatic hydrocarbons or its mixture, for example pentane, hexane, heptane, hexanaphthene, toluene or its mixture, preferred hexane, toluene.
Organo-aluminium compound as raw material comprises aluminum alkyls, aluminum alkoxide, aryl aluminium, haloalkyl aluminium etc.Wherein preferred trialkylaluminium, more preferably three (C
1-C
6Alkyl) aluminium, particularly trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, preferably trimethyl aluminium.
The inert atmosphere gases that is adopted during reaction can be nitrogen, helium, methane etc.
The oligomeric aluminoxane products that makes according to the inventive method or for to contain the suspension of glue or floss, or be homogeneous phase solution.This product can directly be used as the promotor of metalloscene catalyst in the olefinic polymerization.If desired, can above-mentioned suspension or solution be concentrated by the method for underpressure distillation or evaporation.This product can be deposited the long period more than two months in inert atmosphere.
Method required equipment of the present invention is simple, easy and simple to handle.Because the existence of emulsifying agent, water can be well dispersed in the inert solvent, so sufficient reacting, productive rate is higher than 95%, favorable reproducibility.The gained reaction product need not further to separate to purify, can directly use, and excellent storage stability.Do not glue reactor wall with oligomeric aikyiaiurnirsoxan beta as the polyolefine that promotor obtains, have good flowability by the inventive method preparation.
Further specify the present invention with embodiment below, but this there is the restriction that is not subjected to these embodiment.
The polyreaction of carrying out among the embodiment has two classes: polymerization under atmospheric pressure and high pressure polymerisation.
Polymerization under atmospheric pressure be will be equipped with 500 milliliters of three-necked bottles of agitator change ethene atmosphere into after purifying with high purity nitrogen, add 100 milliliters of toluene, a certain amount of aikyiaiurnirsoxan beta suspension and a certain amount of Metallocenic compound.Continuing to feed ethene is normal pressure to keep in the bottle, uses the ethanol termination reaction after 0 minute at 40 ℃ of following polyase 13s.Resulting polymers is with washing with alcohol and vacuum-drying.
High pressure polymerisation is in the 1 liter stainless steel autoclave that has purified with high purity nitrogen, adds 300 milliliters of toluene, a certain amount of aikyiaiurnirsoxan beta suspension and a certain amount of Metallocenic compounds in ethene atmosphere.Keeping ethylene pressure is 1.0 MPas, makes it to use the ethanol termination reaction then 45 ℃ of following polymerizations 1 hour.Resulting polymers is with washing with alcohol and vacuum-drying.
Embodiment 1
In 200 ml flasks of magnetic stick are housed, under nitrogen atmosphere, add 100 milliliters of toluene, 0.5 milliliter of polyoxyethylene-sorbitan mono-oleate (commodity are called Span80, and the HLB value is 4.3, Shanghai chemical reagent factory product) and 2 ml waters successively.On magnetic stirrer, stir, obtain emulsion with about 250 rev/mins rotating speed.In 500 milliliters of three-necked bottles of agitator and pneumatic outlet are housed, trimethyl aluminium hexane solution (Tokyo changes into (strain) system) and 50 milliliters of toluene of under nitrogen atmosphere, adding 100 milliliter of 15 heavy %, 0 ℃, fully stir under, above-mentioned emulsion is splashed into wherein Al/H with the rate of addition of about 2 ml/min
2O (mol ratio) is 1.3.Be warming up to 40 ℃ then, continued stirring reaction 4 hours, obtain containing the suspension of adularescent floss.
With bicyclic pentadiene zirconium dichloride (Cp
2ZrCl
2, the Aldrich product) and be Primary Catalysts, be normal pressure and the high pressure polymerisation reaction that promotor carries out ethene with the above-mentioned oligomeric aikyiaiurnirsoxan beta that makes, operating parameters and experimental result are listed in table 1.The fusing point of polymkeric substance records with dsc in the table.
Table 1
What * use is that present embodiment is prepared but placed oligomeric aikyiaiurnirsoxan beta after 60 days herein.
| Polymerization under atmospheric pressure | High pressure polymerisation | ||
| The Metallocenic compound consumption, mole | 3.28×10 -6 | 3.28×10 -6 | 3.28×10 -6 |
| The aikyiaiurnirsoxan beta consumption, milliliter suspension | 10 | 10 - | 20 |
| Al/Zr (mol ratio) | 1707 | 1707 | 3414 |
| Polymerization activity, gram polyethylene/mole zirconium hour | 5.4×10 6 | 5.2×10 6 | 2.0×10 7 |
| Melting point polymer, ℃ | 132.8 | 133.0 | 136.3 |
Embodiment 2
Prepare oligomeric aikyiaiurnirsoxan beta according to embodiment 1 described method, different is to use 3.0 ml waters, and dropping temperature is 9 ℃, Al/H
2O (mol ratio) is 0.8, and the temperature reaction time is 2 hours, obtains containing the suspension of adularescent floss.Separating dried solid productive rate is 98%.
With Cp
2ZrCl
2Being Primary Catalysts, is the polymerization under atmospheric pressure reaction that promotor carries out ethene, wherein Cp with the above-mentioned oligomeric aikyiaiurnirsoxan beta that makes
2ZrCl
2Be respectively 3.28 * 10 with the consumption of oligomeric aikyiaiurnirsoxan beta suspension
-6The mole and 10 milliliters, Al/Zr (mol ratio) is 1707, polymerization activity is 3.4 * 10
6Gram polyethylene/mole zirconium hour, the fusing point of resulting polymers is 133.1 ℃.
Embodiment 3
Prepare oligomeric aikyiaiurnirsoxan beta according to embodiment 1 described method, different is that dropping temperature is 20 ℃, and rate of addition is about 0.9 ml/min, and the temperature reaction time is 3 hours, obtains containing the suspension of adularescent floss.
With Cp
2ZrCl
2Being Primary Catalysts, is the polymerization under atmospheric pressure reaction that promotor carries out ethene, wherein Cp with the above-mentioned oligomeric aikyiaiurnirsoxan beta that makes
2ZrCl
2Be respectively 3.28 * 10 with the consumption of oligomeric aikyiaiurnirsoxan beta suspension
-6The mole and 10 milliliters, Al/Zr (mol ratio) is 1707, polymerization activity is 4.3 * 10
6Gram polyethylene/mole zirconium hour, the fusing point of resulting polymers is 132.7 ℃.
Embodiment 4
Prepare oligomeric aikyiaiurnirsoxan beta according to embodiment 1 described method, different is to use 100 milliliters of hexanes as the inert solvent in the emulsion, replace 50 milliliters of toluene with 50 milliliters of hexanes, dropping temperature is 14 ℃, rate of addition is about 0.9 ml/min, the temperature reaction temperature is 50 ℃, obtains containing the suspension of adularescent floss, and productive rate is 98%.
Respectively with Cp
2ZrCl
2With ethylenebis indenyl zirconium dichloride (Et (Ind)
2ZrCl
2, press J.Orgmet, Chem.288, the method preparation of 63-67 (1985)) and be Primary Catalysts, be the polymerization under atmospheric pressure reaction that promotor carries out ethene with the above-mentioned oligomeric aikyiaiurnirsoxan beta that makes, operating parameters and experimental result are listed in table 2.
Table 2
| The Metallocenic compound consumption, mole | Cp 2ZrCl 2 3.28×10 -6 | Et(Ind) 2ZrCl 2 3.42×10 -6 |
| The aikyiaiurnirsoxan beta consumption, milliliter suspension | 10 | 20 |
| Al/Zr (mol ratio) | 1707 | 3275 |
| Polymerization activity, gram polyethylene/mole zirconium hour | 5.1×10 6 | 7.6×10 6 |
| Melting point polymer, ℃ | 152.9 | 133.5 |
Embodiment 5
Prepare oligomeric aikyiaiurnirsoxan beta according to embodiment 1 described method, different is to use 3.0 ml waters, the trimethyl aluminium hexane solution that replaces 100 milliliter of 15 heavy % with the trimethyl aluminium toluene solution (Aldrich product) of 100 milliliter of 18 heavy %, dropping temperature is 10 ℃, rate of addition is about 1.0 ml/min, Al/H
2O (mol ratio) is 1.2, obtains containing the suspension of oyster white jelly.
Respectively with Cp
2ZrCl
2And Et (Ind)
2Cl
2Being Primary Catalysts, is normal pressure and the high pressure polymerisation reaction that promotor carries out ethene with the above-mentioned oligomeric aikyiaiurnirsoxan beta that makes, and operating parameters and experimental result are listed in table 3.
Table 3
| Polymerization under atmospheric pressure | High pressure polymerisation | ||
| The Metallocenic compound consumption, mole | Cp 2ZrCl 2 3.28×10 -6 | Et(Ind) 2ZrCl 2 3.28×10 -6 | Et(Ind) 2ZrCl 2 3.28×10 -6 |
| The aikyiaiurnirsoxan beta consumption, milliliter suspension | 10 | 20 | 40 |
| Al/Zr (mol ratio) | 2439 | 4678 | 9357 |
| Polymerization activity, gram polyethylene/mole zirconium hour | 5.4×10 6 | 9.1×10 6 | 1.2×10 7 |
| Melting point polymer, ℃ | 134.6 | 131.6 | 134.1 |
Embodiment 6
Prepare oligomeric aikyiaiurnirsoxan beta according to embodiment 1 described method, different is to use 0.3 milliliter of Span-80 and 1.5 ml waters, the trimethyl aluminium hexane solution that replaces 100 milliliter of 15 heavy % with the triethyl aluminum hexane solution (Tokyo changes into (strain) system) of 100 milliliter of 15 heavy %, dropping temperature is 11 ℃, rate of addition is about 0.5 ml/min, Al/H
2O (mol ratio) is 1.1, and the temperature reaction temperature is 60 ℃, obtains containing the suspension of adularescent floss.
Respectively with Cp
2ZrCl
2And Et (Ind)
2ZrCl
2Being Primary Catalysts, is the polymerization under atmospheric pressure reaction that promotor carries out ethene with the above-mentioned oligomeric aikyiaiurnirsoxan beta that makes, and operating parameters and experimental result are listed in table 4.
Table 4
| The Metallocenic compound consumption, mole | Cp 2ZrCl 2 3.28×10 -6 | Et(Ind) 2ZrCl 2 3.42×10 -6 |
| The aikyiaiurnirsoxan beta consumption, milliliter suspension | 50 | 50 |
| Al/Zr (mol ratio) | 5488 | 5263 |
| Polymerization activity, gram polyethylene/mole zirconium hour | 1.9×10 5 | 2.0×10 6 |
| Melting point polymer, ℃ | 128.3 | 128.3 |
Embodiment 7
Prepare oligomeric aikyiaiurnirsoxan beta according to embodiment 1 described method, different is to use 0.3 milliliter of Span-80 and 1.4 ml waters, with the mixed solution of 20 milliliters of triisobutyl aluminiums (Aldrich product) and 80 milliliters of toluene inert solvent solution as aluminum alkyls, dropping temperature is 13 ℃, rate of addition is about 1.0 ml/min, Al/H
2O (mol ratio) is 1.1, and the temperature reaction temperature is 60 ℃, obtains colourless solution.
Respectively with Cp
2ZrCl
2And Et (Ind)
2ZrCl
2Being Primary Catalysts, is the polymerization under atmospheric pressure reaction that promotor carries out ethene with the above-mentioned oligomeric aikyiaiurnirsoxan beta that makes, and operating parameters and experimental result are listed in table 5.
Table 5
| The Metallocenic compound consumption, mole | Cp 2ZrCl 2 3.28×10 -6 | Et(Ind) 2ZrCl 2 3.42×10 -6 |
| The aikyiaiurnirsoxan beta consumption, milliliter suspension | 50 | 50 |
| Al/Zr (mol ratio) | 4878 | 4678 |
| Polymerization activity, gram polyethylene/mole zirconium hour | 4.3×10 5 | 7.3×10 6 |
| Melting point polymer, ℃ | 130.2 | 132.7 |
Claims (10)
1, a kind of preparation method of oligomeric aikyiaiurnirsoxan beta, comprise that the inert solvent solution that makes aluminum alkyls and the emulsion of water/inert solvent react, it is characterized in that: with emulsifying agent water and inert solvent are made water-in-oil emulsion with known emulsification means, wherein inert solvent: water: the volume ratio of emulsifying agent is 100: 0.5～10: 0.1～1; Aluminum alkyls is dissolved in makes the solution that aluminum alkyls concentration is 5～30 heavy % in the inert solvent; In inert atmosphere, stirring down above-mentioned emulsion is that 0.8～2: 1 consumption splashes in the solution of aluminum alkyls according to the mol ratio of water in aluminum alkyls and the emulsion, dropping temperature is-10～40 ℃, rate of addition is 0.2～20 ml/min, after dropwising system is warming up to 40～80 ℃ and reacts 1～4 hour.
2, in accordance with the method for claim 1, it is characterized in that described inert solvent: water: the volume ratio of emulsifying agent is 100: 1～5: 0.2～0.5.
3, in accordance with the method for claim 1, the concentration that it is characterized in that aluminum alkyls is 10～20 heavy %.
4, in accordance with the method for claim 1, the mol ratio that it is characterized in that water in aluminum alkyls and the emulsion is 1～1.5: 1.
5, in accordance with the method for claim 1, it is characterized in that dropping temperature is 0～20 ℃, rate of addition is 0.5～5 ml/min.
6, in accordance with the method for claim 1, the temperature of reaction after it is characterized in that dropwising is 40～60 ℃.
7, in accordance with the method for claim 1, it is characterized in that described emulsifying agent is that hydrophile-lipophile balance value is 2～6 polyalcohols nonionogenic tenside.
8, in accordance with the method for claim 1, it is characterized in that describedly being used for disperse water or dissolving aluminum alkyls inert solvent can be the same or different, they are selected from saturated alkane, naphthenic hydrocarbon, aromatic hydrocarbons or its mixture.
9, in accordance with the method for claim 1, it is characterized in that described aluminum alkyls is selected from trimethyl aluminium or triisobutyl aluminium.
10, in accordance with the method for claim 1, it is characterized in that described inert atmosphere gases is selected from nitrogen, helium, methane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95107483A CN1045446C (en) | 1995-07-14 | 1995-07-14 | Process for producing low-polymer alumin oxyane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95107483A CN1045446C (en) | 1995-07-14 | 1995-07-14 | Process for producing low-polymer alumin oxyane |
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|---|---|
| CN1140715A CN1140715A (en) | 1997-01-22 |
| CN1045446C true CN1045446C (en) | 1999-10-06 |
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|---|---|---|---|
| CN95107483A Expired - Fee Related CN1045446C (en) | 1995-07-14 | 1995-07-14 | Process for producing low-polymer alumin oxyane |
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| CN102190678B (en) * | 2010-03-16 | 2015-07-01 | 大庆石油学院 | Method for preparing modification aluminoxane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0295312A1 (en) * | 1986-12-30 | 1988-12-21 | Mitsui Petrochemical Industries, Ltd. | Solid catalyst for olefin polymerization and process for its preparation |
| EP0405121A2 (en) * | 1989-06-24 | 1991-01-02 | Focke & Co. (GmbH & Co.) | Production plant for making large packages in the form of cartoned packs of groups of small packages of paper handkerchiefs |
-
1995
- 1995-07-14 CN CN95107483A patent/CN1045446C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0295312A1 (en) * | 1986-12-30 | 1988-12-21 | Mitsui Petrochemical Industries, Ltd. | Solid catalyst for olefin polymerization and process for its preparation |
| EP0405121A2 (en) * | 1989-06-24 | 1991-01-02 | Focke & Co. (GmbH & Co.) | Production plant for making large packages in the form of cartoned packs of groups of small packages of paper handkerchiefs |
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|---|---|
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