CN1247495C - Method for preparing 1-decene oligomer by non homogeneous catalysis - Google Patents
Method for preparing 1-decene oligomer by non homogeneous catalysis Download PDFInfo
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- CN1247495C CN1247495C CN 200410000110 CN200410000110A CN1247495C CN 1247495 C CN1247495 C CN 1247495C CN 200410000110 CN200410000110 CN 200410000110 CN 200410000110 A CN200410000110 A CN 200410000110A CN 1247495 C CN1247495 C CN 1247495C
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Abstract
The present invention relates to a method for preparing 1-decene oligomer by a mode of non homogeneous catalysis, which comprises the steps that a 1-decene monomer and a laminar analysis silica gel carrier load Et 2 AlCl are used as catalysts; water or methanol is used as a promoter; the components have the mass ratio of the monomer to the catalysts to the promoter is 10 to 33: 1: 0.015 to 0.020; the components are mixed and stirred and react for 24 hours at the temperature of 0 DEG C. to 54 DEG C.; the catalysts are removed by filtration; then, the 1-decene oligomer is obtained by fractionation and purification. The 1-decene oligomer has the average molecular weight of 650 to 1160 and the molecular weight distribution of 1.32 to 1.81. The present invention has the advantages that the contents of chlorine and fluorine in products can be reduced by the non homogeneous catalysis of a polymerization system; the catalysts and the products can be separated in order to be recovered and reused; the environment pollution is reduced.
Description
Technical field
The present invention relates to a kind of method for preparing poly ﹠ Alpha ,-olefin oil, the particularly method of catalytic preparation 1-decene oligopolymer.
Technical background
The 1-decene oligopolymer is a kind of of poly ﹠ Alpha ,-olefin oil, and poly ﹠ Alpha ,-olefin oil has low condensation point and high viscosity index, and thermal oxidation stability is good, and high temperature evaporation loss is little, to advantages such as the consistency in the susceptibility of additive, fluorine Lyons and electrical insulation capability are good.Because alpha-olefin molecular weight height, segment is difficult for motion, so common free radical polymerisation process can not make the monomer activation produce polymerization.Japanese Patent " butylene and chain alpha-olefin copolymer prepare oligopolymer " (JP08,505,888) discloses the method that a kind of cationoid polymerisation prepares base oil, with AlCl
3, BF
3As catalyzer, preparation gathers 1-decene Deng Lewis acid.This method is owing to adopt homogeneous system, makes AlCl in the product
3, BF
3Content etc. halides is higher, can't produce the product of low halides, BF
3Not only very expensive but also because the corrodibility of fluorine, and cause a series of environmental problem.Because catalyzer is difficult to separate, and can't reclaim use, has produced a large amount of reluctant production waste liquids, therefore improved production cost.Simultaneously, the poly-alpha olefins molecular weight that is obtained is low, and resulting oil body is also lower, does not reach environmental standard when using as lubricating oil.So these class methods have much room for improvement at present.In addition, in preparing the method for poly ﹠ Alpha ,-olefin oil, adopt chrome catalysts in addition, for example: " hydrocarbon lubricating oil and fuel oil pour point reducer and viscosity index improver " (Japanese patent application publication No. JP09,508,151); Adopt Ziegler type catalyzer, for example: " preparation alpha-olefin oligopolymer " (Japanese patent application publication No. JP07,133,234).These method common deficiencies are that used catalyzer costs an arm and a leg, and the activity of polyreaction is not high, need to introduce ethene.In addition, owing to, its application is restricted with the weight-average molecular weight instability of the polymkeric substance of these method gained.
Summary of the invention
The object of the present invention is to provide the novel method of preparation 1-decene oligopolymer.This method makes catalyzer can separate, recycle and reuse with product by heterogeneousization of polymerization system, reduces environmental pollution; Can obtain the high poly ﹠ Alpha ,-olefin oil of quality.
A kind of heterogeneous catalysis of the present invention prepares the method for 1-decene oligopolymer, is with 1-decene monomer, the carrier loaded Et of chromatographic silica gel
2The catalyzer of AlCl, do promotor with water or methyl alcohol, the mass ratio of each component is a monomer: catalyzer: promotor=10～33: 1: 0.015～0.020, under 0～54 ℃ condition, each component was mixed stirring reaction 24 hours, remove by filter catalyzer, purifying through fractionation obtains the 1-decene oligopolymer again.
The used Preparation of catalysts method of the present invention is as follows:
1),, be stored in the nitrogen standby in 300～700 ℃ of sintering 15 hours with the chromatographic silica gel carrier of 20～60 ;
2) the chromatographic silica gel carrier of above-mentioned processing and inert water-free organic solvent are mixed, add mass concentration again and be 26% Et
2The inert water-free organic solution of AlCl under room temperature, pressure 1.5atm condition, mixed 1 hour, removed impurity in the solution with the inert water-free organic solvent washing, and drying is removed the inert water-free organic solvent under vacuum condition, obtains the chromatographic silica gel catalyzer; Chromatographic silica gel and Et
2The mass ratio of AlCl is 10: 1.3.
When the present invention prepared catalyzer, the sintering temperature of chromatographic silica gel carrier the best was 600 ℃.
When the present invention prepared catalyzer, the inert water-free organic solvent was: n-pentane, n-hexane or n-heptane.
The present invention is according to the cationic oligomer reaction principle, adopts Lewis acid catalyst and promotor to form the complex catalysis system.Select Et for use
2AlCl requires to guarantee that at reaction conditions organo-metallic halogenide can react with a certain proportion of oh group on the chromatographic silica gel carrier surface at least.Its reaction formula is as follows:
The present invention passes through Et
2The hydroxyl of AlCl and chromatographic silica gel carrier surface reacts, and removes the ethane that reaction produces, and forms the load Lewis acid catalyst with the chemical bond combination.Simultaneously with the promotor of halide not as proton donor, form Lewis acid complex catalysis system.By selection, make the pure inclusion-free of catalyzer to solvent and promotor.Support of the catalyst adopts porous material certain intensity, higher specific surface area, requires material surface that the oh group of some amount is arranged, and in order to the organic group in the replacement catalyzer, thereby forms load.
The present invention is the method by catalyst cupport, reaches the purpose of catalyzer and product separation, separates easily, and good separating effect has fundamentally been avoided halid existence in the product simultaneously.
Chromatographic silica gel carrier of the present invention is calcined in rare gas element, and rare gas element is for example used nitrogen, and sintering temperature can be at 300 ℃～700 ℃.Sintering temperature is too high, will cause the serious disappearance of hydroxy functional group in the carrier; Sintering temperature is low excessively, can't remove the physical bond water in the carrier.Sintering temperature is preferably 600 ℃, and the carrier hydroxy radical content is stable under this temperature, easily the consumption of control catalyst.
Carrier is wanted earlier and suitable inert water-free organic solvent combination, forms slurry.Slurry combines with organo-metallic halogenide more then.Used inert water-free organic solvent requires that carrier and the halid reaction of organo-metallic are not had influence substantially, is easy to simultaneously remove by physical means.Inert water-free organic solvent well-known in the art, commonly used has the alkane that is in a liquid state under standard state, for example: n-pentane, n-hexane or n-heptane.Can adopt commercially available inert water-free organic solvent, for example: commercially available anhydrous n-hexane, the water content of this product is 50ppm.If water content is too high in the inert water-free organic solvent, will cause the poisoning of catalyst inactivation.
The temperature of 1-decene oligomerisation reaction of the present invention is: 0 ℃～54 ℃ of temperature, be preferably 16 ℃, and the oligomerisation temperature is too high, will make oligomerisation reaction drop to side reaction, and the polymerization degree can reduce; Temperature is low excessively, and then oligomerisation reaction speed is slow excessively.
The present invention can reduce chlorine, fluorine content in the product by heterogeneousization of polymerization system, makes catalyzer can separate, recycle and reuse with product, reduces environmental pollution.
The 1-decene oligopolymer molecular-weight average that the present invention obtains meets lubricant base molecular weight claimed range 650～1160, and molecular weight distribution is 1.32～1.81, the quality height of oil product.
Specific embodiment
Embodiment A, B, C are the embodiment that the present invention prepares catalyzer.
Embodiment 1～23rd, and the present invention prepares the embodiment of 1-decene oligopolymer.
Embodiment A
Getting 10g chromatographic silica gel aperture is 20～60 , in 600 ℃ of sintering 15 hours, at stove internal cooling to 200 ℃, moves into vacuum drier, stand-by.Get the sealing of 100ml dried and clean polymerization bottle,, vacuumize, fill high pure nitrogen, air pressure 1.5atm with the gas burner heating.Make to keep inert gas environment in the polymerization bottle, standby.
In the polymerization bottle of 100ml, add the silica gel and the 40ml anhydrous n-hexane of above-mentioned processing.Then, adding mass concentration with syringe is 26% Et
2AlCl hexane solution 5g.After stirring 1 hour at ambient temperature,, remove the impurity in the solution with the anhydrous n-hexane washing of 20ml.Gained solid drying under room temperature, vacuum condition was removed and is desolvated in 10 hours, obtained the load silica-gel catalyst.With HITACHIE-8000 type atomic absorption spectrometry aluminium content, obtaining catalyst cupport efficient is 0.01g (Al)/g (supported catalyst).
Embodiment B
The same embodiment A of working method, different is that sintering temperature is 700 ℃, catalyst cupport efficient is 0.011g (Al)/g (supported catalyst).
Embodiment C
The same embodiment A of working method, different is that sintering temperature is 300 ℃, catalyst cupport efficient is 0.027g (Al)/g (supported catalyst).
Embodiment 1
Keeping under the inert atmosphere conditions, with the mass ratio of monomer and catalyzer and promotor 33: 1: 0.015, in the sealing polymerization bottle of 100ml dried and clean, by the method that is connected with another polymerization bottle, the obtained supported catalyst of embodiment A of adding 0.66g; With syringe the decene monomer of 30ml and the mixture of 0.01g water are injected this polymerization bottle simultaneously again, under 16 ℃ of conditions of water-bath, stir polymerization 24 hours.After filtration, purification obtains product 1-decene oligopolymer.Transformation efficiency 89.98%, molecular-weight average 1053, molecular weight distribution 1.32, limiting viscosity 2.32.
Embodiment 2
Working method is with embodiment 1, and different is, and to change monomer and catalyst quality ratio be to carry out polymerization at 30: 1.Transformation efficiency 48.98%, molecular-weight average 1123, molecular weight distribution 1.32, limiting viscosity 3.35.
Embodiment 3
Working method is with embodiment 1, and different is, and to change monomer and catalyst quality ratio be to carry out polymerization at 25: 1.Transformation efficiency 54.68%, molecular-weight average 1133, molecular weight distribution 1.32, limiting viscosity 3.18.
Embodiment 4
Working method is with embodiment 1, and different is, and to change monomer and catalyst quality ratio be to carry out polymerization at 20: 1.Transformation efficiency 48.41%, molecular-weight average 1146, molecular weight distribution 1.32, limiting viscosity 3.56.
Embodiment 5
Working method is with embodiment 1, and the mass ratio that different is changes monomer and catalyzer is to carry out polymerization at 10: 1.Transformation efficiency 72.12%, molecular-weight average 1164, molecular weight distribution 1.32, limiting viscosity 3.50.
Embodiment 6
Working method is with embodiment 1, and different is to adopt the obtained supported catalyst of Embodiment B, changes monomer and catalyst quality ratio and is 30: 1 and carry out polymerization.Transformation efficiency 54.48%, molecular-weight average 850, molecular weight distribution 1.63, limiting viscosity 2.56.
Embodiment 7
Working method is with embodiment 1, and different is to adopt methyl alcohol to cook reaction promotor to carry out polymerization, the mass ratio of change monomer and catalyzer and promotor 30: 1: 0.02.Transformation efficiency 34.14%, molecular-weight average 1095, molecular weight distribution 1.32, limiting viscosity 3.03.
Embodiment 8
Working method is with embodiment 1, and different is to adopt methyl alcohol to cook reaction promotor to carry out polymerization, the mass ratio of change monomer and catalyzer and promotor 20: 1: 0.02.Transformation efficiency 78.86%, molecular-weight average 1109, molecular weight distribution 1.32, limiting viscosity 1.62.
Embodiment 9
Working method is with embodiment 1, and different is to adopt methyl alcohol to cook reaction promotor to carry out polymerization, the mass ratio of change monomer and catalyzer and promotor 10: 1: 0.02.Transformation efficiency 45.11%, molecular-weight average 1109, molecular weight distribution 1.32, limiting viscosity 2.74.
Embodiment 10
Working method is with embodiment 1, and the mass ratio that different is changes monomer and catalyzer is 30: 1, carries out polymerization under 0 ℃.Transformation efficiency 59.46%, molecular-weight average 654, molecular weight distribution 1.45.
Embodiment 11
Working method is with embodiment 1, and the mass ratio that different is changes monomer and catalyzer is 30: 1, carries out polymerization under 16.0 ℃.Transformation efficiency 89.89%, molecular-weight average 1053, molecular weight distribution 1.34, limiting viscosity 2.32.
Embodiment 12
Working method is with embodiment 1, and the mass ratio that different is changes monomer and catalyzer is 30: 1, carries out polymerization under 53.2 ℃.Transformation efficiency 73.69%, molecular-weight average 1012, molecular weight distribution 1.28, limiting viscosity 2.15.
Embodiment 13
Working method is with embodiment 1, and different is to adopt methyl alcohol to cook reaction promotor to carry out polymerization, and the mass ratio of change monomer and catalyzer and promotor 30: 1: 0.02 carries out polymerization under 18.6 ℃.Transformation efficiency 54.68%, molecular-weight average 1133, molecular weight distribution 1.32, limiting viscosity 3.18.
Embodiment 14
Working method is with embodiment 1, and different is to adopt methyl alcohol to cook reaction promotor to carry out polymerization, and the mass ratio of change monomer and catalyzer and promotor 30: 1: 0.02 carries out polymerization under 24.0 ℃.Transformation efficiency 53.08%, molecular-weight average 846, limiting viscosity 2.09.
Embodiment 15
Working method is with embodiment 1, and different is to adopt methyl alcohol to cook reaction promotor to carry out polymerization, and the mass ratio of change monomer and catalyzer and promotor 30: 1: 0.02 carries out polymerization under 36.1 ℃.Transformation efficiency 34.14%, molecular-weight average 1095, limiting viscosity 1.62.
Embodiment 16
Working method is with embodiment 1, and different is to adopt methyl alcohol to cook reaction promotor to carry out polymerization, and the mass ratio of change monomer and catalyzer and promotor 30: 1: 0.02 carries out polymerization under 68.2 ℃.Transformation efficiency 29.25%, molecular-weight average 672, limiting viscosity 1.92.
Embodiment 17
Working method is with embodiment 1, and different is to adopt the obtained supported catalyst of Embodiment C, changes monomer and catalyst quality ratio and is 30: 1 and carry out polymerization.Transformation efficiency 92.26%, molecular-weight average 967, molecular weight distribution 1.63, limiting viscosity 1.85.
Embodiment 18
Working method is with embodiment 1, and different is to adopt the obtained supported catalyst of Embodiment C, and changing monomer is 30: 1 with the catalyst quality ratio, carries out polymerization under 0 ℃.Transformation efficiency 87.61%, molecular-weight average 967, molecular weight distribution 1.32, limiting viscosity 2.03.
Embodiment 19
Working method is with embodiment 1, and different is to adopt the obtained supported catalyst of Embodiment C, and changing monomer is 30: 1 with the catalyst quality ratio, carries out polymerization under 30 ℃.Transformation efficiency 79.82%, molecular-weight average 903, molecular weight distribution 1.72, limiting viscosity 2.00.
Embodiment 20
Working method is with embodiment 1, and different is to adopt the obtained supported catalyst of Embodiment C, and adopts methyl alcohol to cook reaction promotor and carry out polymerization, the mass ratio of change monomer and catalyzer and promotor 30: 1: 0.02.Transformation efficiency 73.86%, molecular-weight average 842, molecular weight distribution 1.43, limiting viscosity 2.58.
Embodiment 21
Working method is with embodiment 1, and different is to adopt the obtained supported catalyst of Embodiment C, and adopts methyl alcohol to cook reaction promotor and carry out polymerization, and the mass ratio of change monomer and catalyzer and promotor 30: 1: 0.02 carries out polymerization under 0 ℃.Transformation efficiency 82.53%, molecular-weight average 836, molecular weight distribution 1.52, limiting viscosity 2.41.
Embodiment 22
Working method is with embodiment 1, and different is to adopt the obtained supported catalyst of Embodiment C, and adopts methyl alcohol to cook reaction promotor and carry out polymerization, and the mass ratio of change monomer and catalyzer and promotor 30: 1: 0.02 carries out polymerization under 50 ℃.Transformation efficiency 51.32%, molecular-weight average 727, molecular weight distribution 1.81, limiting viscosity 1.52.
Embodiment 23
Working method is with embodiment 1, and different is to adopt the obtained supported catalyst of Embodiment C, and adopts methyl alcohol to cook reaction promotor and carry out polymerization, and the mass ratio of change monomer and catalyzer and promotor 30: 1: 0.02 carries out polymerization under 0 ℃.Transformation efficiency 82.53%, molecular-weight average 836, molecular weight distribution 1.52, limiting viscosity 2.41.
Claims (4)
1, a kind of heterogeneous catalysis prepares the method for 1-decene oligopolymer, is with 1-decene monomer, the carrier loaded Et of chromatographic silica gel
2The catalyzer of AlCl, do promotor with water or methyl alcohol, the mass ratio of each component is a monomer: catalyzer: promotor=10～33: 1: 0.015～0.020, under 0～54 ℃ condition, each component was mixed stirring reaction 24 hours, remove by filter catalyzer, purifying through fractionation obtains the 1-decene oligopolymer again.
2, method according to claim 1 is characterized in that: the Preparation of catalysts method is as follows:
1),, be stored in the nitrogen standby in 300～700 ℃ of sintering 15 hours with the chromatographic silica gel carrier of 20～60 ;
2) the chromatographic silica gel carrier of above-mentioned processing and inert water-free organic solvent are mixed, add mass concentration again and be 26% Et
2The inert water-free organic solution of AlCl under room temperature, pressure 1.5atm condition, mixed 1 hour, removed impurity in the solution with the inert water-free organic solvent washing, and drying is removed the inert water-free organic solvent under vacuum condition, obtains the chromatographic silica gel catalyzer; Chromatographic silica gel and Et
2The mass ratio of AlCl is 10: 1.3.
3, method according to claim 2 is characterized in that: the sintering temperature of chromatographic silica gel carrier is 600 ℃.
4, method according to claim 2 is characterized in that: the inert water-free organic solvent is: n-pentane, n-hexane or n-heptane.
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|---|---|---|---|
| CN 200410000110 CN1247495C (en) | 2004-01-05 | 2004-01-05 | Method for preparing 1-decene oligomer by non homogeneous catalysis |
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| CN 200410000110 CN1247495C (en) | 2004-01-05 | 2004-01-05 | Method for preparing 1-decene oligomer by non homogeneous catalysis |
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| CN1247495C true CN1247495C (en) | 2006-03-29 |
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| CN103100419B (en) * | 2011-11-09 | 2015-04-15 | 中国石油化工股份有限公司 | Mixed decene oligomerization catalyst |
| CN106881119B (en) * | 2015-12-16 | 2019-08-02 | 中国石油天然气股份有限公司 | Catalyst for poly α -olefin synthetic oil and preparation method thereof |
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