CN103193902B - A kind of preparation method of ethylene oligomer - Google Patents
A kind of preparation method of ethylene oligomer Download PDFInfo
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- CN103193902B CN103193902B CN201210005406.XA CN201210005406A CN103193902B CN 103193902 B CN103193902 B CN 103193902B CN 201210005406 A CN201210005406 A CN 201210005406A CN 103193902 B CN103193902 B CN 103193902B
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Abstract
The present invention relates to a kind of preparation method of ethylene oligomer, it is characterized in that adopting rotating disk reactor to be prepared, catalyzer adopts post-transition metal catalyst system, by catalyzer, thinner, the mixed solution metering of promotor and comonomer is pumped in rotating disk reactor, feeding rate 0.1ml/s-1L/s, reactor is heated to temperature required after, pass into ethene, start rotating disk, temperature of reaction controls between-70-200 DEG C, pressure 1bar-60bar, polymerization reaction time is 3s-6000s, the rotary speed 3000-5000rpm of reactor is controlled in reaction process, the residence time of material on rotating disk is 0.1-5s, after reaction terminates, be separated, obtain ethylene oligomer.Compared with being polymerized with traditional stirring, the mean residence time of material in rotating disk reactor at least shortens more than 30 times, and energy consumption is low, production efficiency is high.Especially be applicable to the polymerization temperature accurately controlling polymerization process each stage in initial polymerization strong exothermal reaction involved in the present invention, significantly improve selectivity and the yield of catalyst activity and C8-C24 alpha-olefin.
Description
Technical field
The present invention relates to a kind of preparation method of ethylene oligomer, specifically rotating disk reactor is used for field of olefin polymerisation by one, prepares the method for ethylene oligomer.
Background technology
Ethylene oligomer is the ethene polymers that molecular weight is less than 1000g/mol, and wherein the alhpa olefin of C8-C24 is important high-end lube product additive.Gibson etc. and Brookhart etc. find that the pyridine diimine title complex of Fe (II) and Co (II) can catalyzed ethylene polymerization (J.Chem.Commun.1998 such as GibsonVC, 849 efficiently simultaneously; WO99/12981,1999; The J.Am.ChemSoc.1998 such as BrookhartM, 120,4049; BennettAMAWO98/27124,1998).Patent ZL200910101039.1 discloses a kind of catalyst system for vinyl polymerization, can obtain a series of products from ethylene oligomer to ultrahigh molecular weight polyethylene(UHMWPE) by change pyridine diimine ligand structure.Wherein, in ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 50-70%.Patent CN1142142C and patent CN1179982 discloses the late transition metal catalyst based on pyridine diimine ligand structure, polymerisate is mainly ethylene oligomer, in polymerization process, product is dissolved in thinner toluene, system becomes the feature of polymerization in homogeneous phase, and the molar percentage of C8-C20 alpha-olefin is 55-75%.In the late transition metal catalyst producing ethylene oligomer at present, ubiquitous phenomenon is that catalyst activity is high, especially in the polyreaction starting stage, active abrupt release, produce a large amount of heat of polymerization (be Ziegler-Natta, the heat release of metallocene catalyst polymerisation starting stage 5-10 doubly), traditional heat-removing way (as water of condensation, cool brine etc.) can not the balance of maintenance system temperature, brings the unmanageable problem of initial polymerization stage polymerization temperature.And concerning this type of catalyzer, polymerization temperature more low polymerization activity is higher, and the alpha-olefin selectivity of C8-C20 is higher.If control inaccurate to polymerization initial temperature, bring negative impact by the distribution of polymerisate, this has higher requirement to the mass transfer in polymerization process, heat-transfer effect.
Rotating disk reactor is a kind of reactor technology of process intensification.This technology makes fluid prolong axial distribution on rotating disk by atwirl rotating disk, and form the liquid film of very thin thickness, this thin film mass transfer, heat-transfer effect are splendid.Patent CN101081878B adopts rotating disk reactor to prepare hydrogenated nitrile-butadiene rubber.The method is compared with the method preparing hydrogenated nitrile-butadiene rubber of routine, and reaction conditions requires low, enhances the heat-transfer effect of process, significantly reduces the cost of hydrogenation process.Patent US7683142 discloses the method utilizing rotating disk reactor to carry out letex polymerization, can carry out homogeneous phase and heterogeneous emulsion polymerization, prepare evengranular polymer beads by rotating disk reactor technology that is single or combination.AlaviSM etc. (JournalofAppliedPolymerScience, 2009,113,709 – 715) carry out cinnamic bulk polymerization in rotating disk reactor.Rotating disk reactor significantly improves speed of reaction, transformation efficiency.But, not yet find the rotating disk reactor technology for the preparation of ethylene oligomer in current published document.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of ethylene oligomer, rotating disk reactor is adopted to be prepared, greatly enhance the mass transfer in polymerization process, heat transfer and microcosmic mixing, what improve the polymerization initial stage moves heat energy power, thus proposes that a kind of efficiency is high, energy consumption is low and the preparation method of the ethylene oligomer that olefin conversion is higher.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method of ethylene oligomer, it is characterized in that adopting rotating disk reactor to be prepared, catalyzer adopts post-transition metal catalyst system, by catalyzer, thinner, the mixed solution metering of promotor and comonomer is pumped in rotating disk reactor, feeding rate 0.1ml/s-1L/s, reactor is heated to temperature required after, pass into ethene, start rotating disk, polymeric reaction temperature controls between-70-200 DEG C, pressure 1bar-60bar, polymerization reaction time is 3s-6000s, the rotary speed 3000-5000rpm of reactor is controlled in reaction process, the residence time of material on rotating disk is 0.1-5s, after reaction terminates, be separated, obtain ethylene oligomer.
As preferably, described rotating disk reactor is 1 or 2-10 reactors in series, the disk diameter 8-50cm of rotating disk reactor, preferred 15-30cm; Rotating speed is 10,000rpm to the maximum, preferred 800-10,000rpm; Shearing force is 1kwm
2/ K-30kwm
2/ K, preferred 10-15kwm
2/ K.
As preferably, described post-transition metal catalyst system comprises: a) pyridine diimine part; B) methyl ethyl diketone salt compound or halide salt compound; The ratio of both amount of substances is 100 ~ 0.01, and described promotor is the product of the partial hydrolysis of alkylaluminium cpd or alkylaluminium cpd, and the ratio of the amount of substance of described promotor and methyl ethyl diketone salt compound is 100 ~ 10000.
Described methyl ethyl diketone salt compound is ferric acetyl acetonade (Fe (acac)
n) or acetylacetone cobalt (Co (acac)
n), n=2,3, halide salt compound is FeX
nor CoX
n, wherein n=2,3, X are F, Cl, Br or I.
Preferred again, described catalyzer is homogeneous catalyst or heterogeneous catalyst, and wherein the diameter of heterogeneous catalyst is between 100nm-50um, the carrier be suitable for comprise solid, particle, have and be greater than 50m
2g
-1the metal oxide with high-specific surface area, nonmetal oxide, organism or its mixture, when using heterogeneous catalyst, before polyreaction, first by heterogeneous catalyst uniform application on rotating disk.
Described comonomer is C
1-C
20alpha-olefin, can add or not add during polymerization, preferably do not add.
Preferably, described thinner is inertia alkane diluent, comprises the mixture of one or both and the above composition in the alkane of benzene,toluene,xylene, perhydronaphthalene or C6-C12.Preferably to the good thinner of ethylene oligomer dissolving power as toluene, dimethylbenzene, perhydronaphthalene, normal heptane, octane etc.
Improve, described feeding rate is preferably 0.1ml/s-100ml/s again, and polymerization temperature is preferably-40-100 DEG C, and polymerization pressure is preferably 1bar-21bar, and polymerization reaction time is preferably 10s-3000s, and the residence time of material on rotating disk is preferably 1s-3s.
Finally, the carrier of described heterogeneous catalyst is preferably the inorganic carrier of silicon-dioxide, aluminum oxide, Thorotrast, titanium dioxide, silica-alumina, silicon carbide, illiteracy holder soil and their compositions.
Compared with prior art, the invention has the advantages that: have employed rotating disk reactor, due to the high speed rotating of reactor inner rotary table, make reaction mass on rotating disk, form the very thin reactive film of one deck, huge shearing force can be produced, show and excellently move thermal effect, and reach microcosmic admixture completely fast.Compared with being polymerized with traditional stirring, the mean residence time of material in rotating disk reactor at least shortens more than 30 times, and energy consumption is low, production efficiency is high.Especially be applicable to the polymerization temperature accurately controlling polymerization process each stage in initial polymerization strong exothermal reaction involved in the present invention, significantly improve selectivity and the yield of catalyst activity and C8-C24 alpha-olefin.
figure of description
Fig. 1 is the structural representation of rotating disk reactor of the present invention;
1. temperature control tank, 2. reactor, 3. rotating disk, 4. rotation axis, 5. gas feed pipe, 6. liquid feeding pipeline, 7. drainage conduit;
Fig. 2 is typical ethylene oligomerization products distribution figure.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
The operation of all air-sensitive materials all adopts standard vacuum double line anhydrous and oxygen-free working method.Agents useful for same uses after all needing refinement treatment.
Product liquid part first qualitative test on Gc/ms Analyser NicoletHPGC6890/MS5973 in oligomerisation experiment.
In oligomerisation experiment, the content of each component of Product liquid part (sample should without suspended solid) measures on gas chromatograph Agilent68090N.Each component be 1 containing the correction factor measuring Olefin Hydrocarbon Homologous Compound, adopt the calibration curve of 1-hexene and normal heptane to calculate.Pillar flow rate of carrier gas 3.0mlmin during measurement
-1, starting temperature 50 DEG C, constant temperature 5min, then 20 DEG C/min is raised to 270 DEG C.
Above-mentioned implementation process according to the known measure of professional, can adopt the mode of continuous feeding or adopts the mode of batch feed.
Embodiment 1
Vinyl polymerization, in 250ml glass reactor, adds 100ml toluene, constant temperature to 30 DEG C.Add 2umol2 again, 6-bis-(1-(2-aminotoluene base ethyl)) pyridine (L), 2umol ferric acetyl acetonade and 3000umolMAO.Under agitation pass into ethylene gas, ethylene pressure is normal pressure, reacts 30 minutes.And the interior mark added when 1ml normal heptane measures as GC (gas-chromatography).Sample centrifugation after-18 DEG C of cold 4h, Product liquid part is preserved in refrigerator, and solid part adds the ethanol solution hydrochloride of 10%, and with after washing with alcohol in vacuum drying oven dry 12h at 50 DEG C.Be polymerized in initial 5min, temperature rises to 65 DEG C from 30 DEG C.This reactive behavior is 3.967 × 10
6g polyethylene/(molFehatm).Typical oligomerization product distribution plan as shown in Figure 2.In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 70%.
Embodiment 2
Vinyl polymerization, in 250ml glass reactor, adds 100ml toluene, constant temperature to 0 DEG C.Add 2umol2 again, 6-bis-(1-(2-aminotoluene base ethyl)) pyridine, 2umol ferric acetyl acetonade and 3000umolMAO.Under agitation pass into ethylene gas, ethylene pressure is normal pressure, reacts 30 minutes.And the interior mark added when 1ml normal heptane measures as GC (gas-chromatography).Sample centrifugation after-18 DEG C of cold 4h, Product liquid part is preserved in refrigerator, and solid part adds the ethanol solution hydrochloride of 10%, and with after washing with alcohol in vacuum drying oven dry 12h at 50 DEG C.Be polymerized in initial 5min, temperature rises to 65 DEG C from 0 DEG C.This reactive behavior is 5.967 × 10
6g polyethylene/(molFehatm).Typical oligomerization product distribution plan as shown in Figure 2.In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 80%.
Embodiment 3
Vinyl polymerization, in 250ml glass reactor, adds 100ml toluene, constant temperature to 50 DEG C.Add 2umol2 again, 6-bis-(1-(2-aminotoluene base ethyl)) pyridine, 2umol ferric acetyl acetonade and 3000umolMAO.Under agitation pass into ethylene gas, ethylene pressure is normal pressure, reacts 30 minutes.And the interior mark added when 1ml normal heptane measures as GC (gas-chromatography).Sample centrifugation after-18 DEG C of cold 4h, Product liquid part is preserved in refrigerator, and solid part adds the ethanol solution hydrochloride of 10%, and with after washing with alcohol in vacuum drying oven dry 12h at 50 DEG C.Be polymerized in initial 5min, temperature rises to 80 DEG C from 50 DEG C.This reactive behavior is 1.324 × 10
6g polyethylene/(molFehatm).Typical oligomerization product distribution plan as shown in Figure 2.In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 65%.
Embodiment 4
The rotating disk reactor schematic diagram that the present embodiment adopts as shown in Figure 1.Disk diameter is 20cm
At 100 DEG C, purge reaction unit with high pure nitrogen, be cooled to 30 DEG C except after the empty G&W in dereaction dress.100ml toluene, 2umol2,6-bis-(1-(2-aminotoluene base ethyl)) pyridine, 2umol ferric acetyl acetonade and 3000umolMAO are fully mixed, constant temperature to 30 DEG C, send into rotating disk reactor.Adjustment rotating is 4000rpm, incision ethene, and reaction pressure is normal pressure, starts polyreaction.Material mean residence time is less than 3s, material is sent into products pot with the speed of 10ml/min and adds terminator.Subsequently, sample centrifugation after-18 DEG C of cooling 4h, Product liquid part is preserved in refrigerator, and solid part adds the ethanol solution hydrochloride of 10%, and with after washing with alcohol in vacuum drying oven dry 12h at 50 DEG C.In polymerization process, temperature fluctuation is in ± 0.5 DEG C.This reactive behavior is 2.427 × 10
7goligomer/ (molFehatm).In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 90%.
Embodiment 5
The rotating disk reactor schematic diagram that the present embodiment adopts as shown in Figure 1.Disk diameter is 20cm
At 100 DEG C, purge reaction unit with high pure nitrogen, be cooled to 0 DEG C except after the empty G&W in dereaction dress.100ml toluene, 2umol2,6-bis-(1-(2-aminotoluene base ethyl)) pyridine, 2umol ferric acetyl acetonade and 3000umolMAO are fully mixed, constant temperature to 0 DEG C, send into rotating disk reactor.Adjustment rotating is 4000rpm, incision ethene, and reaction pressure is normal pressure, starts polyreaction.Material mean residence time is less than 3s, material is sent into products pot with the speed of 10ml/min and adds terminator.Subsequently, sample centrifugation after-18 DEG C of cold 4h, Product liquid part is preserved in refrigerator, and solid part adds the ethanol solution hydrochloride of 10%, and with after washing with alcohol in vacuum drying oven dry 12h at 50 DEG C.In polymerization process, temperature fluctuation is in ± 0.1 DEG C.This reactive behavior is 6.317 × 10
7goligomer/ (molFehatm).In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 96%.
Embodiment 6
The rotating disk reactor schematic diagram that the present embodiment adopts as shown in Figure 1.Disk diameter is 20cm
At 100 DEG C, purge reaction unit with high pure nitrogen, be cooled to 50 DEG C except after the empty G&W in dereaction dress.100ml toluene, 2umol2,6-bis-(1-(2-aminotoluene base ethyl)) pyridine, 2umol ferric acetyl acetonade and 3000umolMAO are fully mixed, constant temperature to 50 DEG C, send into rotating disk reactor.Adjustment rotating is 4000rpm, incision ethene, and reaction pressure is normal pressure, starts polyreaction.Material mean residence time is less than 3s, material is sent into products pot with the speed of 10ml/min and adds terminator.Subsequently, sample centrifugation after-18 DEG C of cold 4h, Product liquid part is preserved in refrigerator, and solid part adds the ethanol solution hydrochloride of 10%, and with after washing with alcohol in vacuum drying oven dry 12h at 50 DEG C.In polymerization process, temperature fluctuation is in ± 0.1 DEG C.This reactive behavior is 2.939 × 10
7goligomer/ (molFehatm).In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 87%.
Embodiment 7
The rotating disk reactor schematic diagram that the present embodiment adopts as shown in Figure 1.Disk diameter is 20cm
At 100 DEG C, purge reaction unit with high pure nitrogen, be cooled to-30 DEG C except after the empty G&W in dereaction dress.100ml toluene, 2umol2,6-bis-(1-(2-aminotoluene base ethyl)) pyridine, 2umol ferric acetyl acetonade and 3000umolMAO are fully mixed, constant temperature, to-30 DEG C, sends into rotating disk reactor.Adjustment rotating is 4000rpm, incision ethene, and reaction pressure is normal pressure, starts polyreaction.Material mean residence time is less than 3s, material is sent into products pot with the speed of 10ml/min and adds terminator.Subsequently, sample centrifugation after-18 DEG C of cold 4h, Product liquid part is preserved in refrigerator, and solid part adds the ethanol solution hydrochloride of 10%, and with after washing with alcohol in vacuum drying oven dry 12h at 50 DEG C.In polymerization process, temperature fluctuation is in ± 0.1 DEG C.This reactive behavior is 8.459 × 10
7goligomer/ (molFehatm).In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 98.57%.
Embodiment 8
The rotating disk reactor schematic diagram that the present embodiment adopts as shown in Figure 1.Disk diameter is 30cm
At 100 DEG C, purge reaction unit with high pure nitrogen, be cooled to-30 DEG C except after the empty G&W in dereaction dress.100ml toluene, 2umol2,6-bis-(1-(2-aminotoluene base ethyl)) pyridine, 2umol ferric acetyl acetonade and 3000umolMAO are fully mixed, constant temperature, to-30 DEG C, sends into rotating disk reactor.Adjustment rotating is 4000rpm, incision ethene, and reaction pressure is normal pressure, starts polyreaction.Material mean residence time is less than 5s, material is sent into products pot with the speed of 10ml/min and adds terminator.Subsequently, sample centrifugation after-18 DEG C of cold 4h, Product liquid part is preserved in refrigerator, and solid part adds the ethanol solution hydrochloride of 10%, and with after washing with alcohol in vacuum drying oven dry 12h at 50 DEG C.In polymerization process, temperature fluctuation is in ± 0.1 DEG C.This reactive behavior is 7.459 × 10
7goligomer/ (molFehatm).In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 97.57%.
Embodiment 9
Except rotary speed is 800rpm, all the other experiment conditions are identical with embodiment 5.In polymerization process, temperature fluctuation is in ± 0.1 DEG C.This reactive behavior is 4.317 × 10
7goligomer/ (molFehatm).In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 93.5%.
Embodiment 10
Outside rotary speed is 10,000rpm, all the other experiment conditions are identical with embodiment 5.In polymerization process, temperature fluctuation is in ± 0.1 DEG C.This reactive behavior is 4.317 × 10
7goligomer/ (molFehatm).In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 96.5%.
Embodiment 11
Adopt 2 rotating disk reactors in series, enter after reactor 1 discharging in reactor 2 and continue reaction.Every group reaction device operation regulates identical with embodiment 5, and material residence time in each reactor is 3s.In polymerization process, temperature fluctuation is in ± 0.1 DEG C.Calculate known with product in second reactor, this reactive behavior is 3.517 × 10
7goligomer/ (molFehatm).In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 96.9%.
Embodiment 12
Adopt 10 rotating disk reactors in series, enter after reactor 1 discharging in reactor 2 and continue reaction, enter next stage reactor successively.Every group reaction device operation regulates identical with embodiment 5, and material residence time in each reactor is 3s.In polymerization process, temperature fluctuation is in ± 0.1 DEG C.Calculate known with product in the 10th reactor, this reactive behavior is 3.817 × 10
7goligomer/ (molFehatm).In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 98.9%.
Embodiment 13
Adopt 1 rotating disk reactor with circulation device, again sent into the liquid material import of reactor 1 after reactor 1 discharging by recycle pump, all the other operations regulate identical with embodiment 5.Material is each, and the residence time is 3s in the reactor.Polymerization carries out 10min altogether.In polymerization process, temperature fluctuation is in ± 0.1 DEG C.This reactive behavior is 4.817 × 10
7goligomer/ (molFehatm).In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 98.4%.
Embodiment 14
Adopt 1 rotating disk reactor with circulation device, again sent into the liquid material import of reactor 1 after reactor 1 discharging by recycle pump, all the other operations regulate identical with embodiment 5.Material is each, and the residence time is 3s in the reactor.Polymerization carries out 30min altogether.In polymerization process, temperature fluctuation is in ± 0.1 DEG C.This reactive behavior is 4.317 × 10
7goligomer/ (molFehatm).In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 98.9%.
Embodiment 15
The loaded catalyst of preparation containing part 2,6-bis-(1-(2-aminotoluene base ethyl)) pyridine.Use following silica-gel carrier in the present embodiment:
955 of Grace company production, median size is 40 microns, following activation before using:
150Kg silica gel 955 (Grace company) is added in activation furnace, under gas speed is the nitrogen gas stream of 0.24m/s, activation furnace temperature is risen to 120 DEG C, constant temperature is after 2 hours, be warming up to 600 DEG C by the speed of 50 DEG C/h, constant temperature 4 hours, is then cooled to envrionment temperature at this temperature.The Silica Surface hydroxy radical content processed is between 0.5-0.7mmol/g.Be stored in dry bottle stand-by under nitrogen protection.
The clean Schlenk catalyzer bottle that magnetic stir bar is housed of drying is vacuumized, roasting 20 minutes are taken out with alcohol blast burner, and be filled with high pure nitrogen and repeatedly take a breath, then the Davison955 silica gel of 1g through thermal activation is loaded, add the toluene solution that 50ml is dissolved with a certain amount of catalyzer (Fe (acac) 3/L), at room temperature stir 12.Vacuum takes toluene solvant away after completion of the reaction.Then add a certain amount of MAO (concentration is the MAO toluene solution of 1.5mol/L), stirred at ambient temperature 2h, vacuum-drying, to the pressed powder of good fluidity, obtains loaded catalyst CatA.Keep for subsequent use under nitrogen atmosphere.
Be aggregated in the rotating disk reactor in embodiment 5 and carry out, before polymerization first by catalyzer uniform application on the rotating pan, all the other experiment conditions are identical with embodiment 5.In polymerization process, temperature fluctuation is in ± 0.1 DEG C.This reactive behavior is 3.817 × 10
6goligomer/ (molFehatm).In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 96.4%.
Embodiment 16
The catalyzer of preparation in selected embodiment 15, other conditions are identical with embodiment 1.In polymerization process, temperature is elevated in 55 DEG C from 30 DEG C.This reactive behavior is 5.817 × 10
5goligomer/ (molFehatm).In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 66.4%.
Embodiment 17
Catalyzer used in embodiment 17 is acetylacetone cobalt, and all the other experiment conditions are in the same manner as in Example 5.In polymerization process, temperature fluctuation is in ± 0.1 DEG C.This reactive behavior is 2.817 × 10
6goligomer/ (molCohatm).In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 93.4%.
Embodiment 18
Catalyzer used in embodiment 18 is iron protochloride, and all the other experiment conditions are in the same manner as in Example 5.In polymerization process, temperature fluctuation is in ± 0.1 DEG C.This reactive behavior is 4.817 × 10
6goligomer/ (molFehatm).In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 95.4%.
Embodiment 19
Add 5ml1-hexene when being polymerized in embodiment 19, all the other polymerizations regulate identical with embodiment 5.In polymerization process, temperature fluctuation is in ± 0.1 DEG C.This reactive behavior is 5.817 × 10
6goligomer/ (molFehatm).In ethylene oligomerization product, the molar percentage of C8-C24 alhpa olefin is 96.4%.
Claims (7)
1. the preparation method of an ethylene oligomer, it is characterized in that adopting rotating disk reactor to be prepared, catalyzer adopts post-transition metal catalyst system, by catalyzer, thinner, the mixed solution metering of promotor and comonomer is pumped in rotating disk reactor, feeding rate 0.1ml/s-1L/s, reactor is heated to temperature required after, pass into ethene, start rotating disk, polymeric reaction temperature controls between-70-200 DEG C, pressure 1bar-60bar, polymerization reaction time is 3s-6000s, the rotary speed 3000-5000rpm of reactor is controlled in reaction process, the residence time of material on rotating disk is 0.1-5s, after reaction terminates, be separated, obtain ethylene oligomer,
Described post-transition metal catalyst system comprises: a) pyridine diimine part; B) methyl ethyl diketone salt compound or halide salt compound; The ratio of both amount of substances is 100 ~ 0.01, and described promotor is the product of the partial hydrolysis of alkylaluminium cpd or alkylaluminium cpd, and the ratio of the amount of substance of described promotor and methyl ethyl diketone salt compound is 100 ~ 10000.
2. preparation method according to claim 1, it is characterized in that described catalyzer is homogeneous catalyst or heterogeneous catalyst, wherein the diameter of heterogeneous catalyst is between 100nm-50um, the carrier be suitable for comprise solid particulate, have and be greater than 50m
2g
-1the metal oxide of high-specific surface area, nonmetal oxide, organism or its mixture.
3. preparation method according to claim 1, is characterized in that described comonomer is C
1-C
20alpha-olefin, can add or not add during polymerization.
4. preparation method according to claim 1, is characterized in that described thinner is the mixture of one or both and above composition in the alkane of benzene,toluene,xylene, perhydronaphthalene or C6-C12.
5. preparation method according to claim 1, it is characterized in that described feeding rate 0.1ml/s-100ml/s, polymerization temperature is-40-100 DEG C, polymerization pressure 1bar-21bar, polymerization reaction time is 10s-3000s, and the residence time of material on rotating disk is 1s-3s.
6. preparation method according to claim 1, is characterized in that described methyl ethyl diketone salt compound is ferric acetyl acetonade Fe (acac)
3or acetylacetone cobalt Co (acac)
n, n=2,3, halide salt compound is FeX
nor CoX
n, wherein n=2,3, X are F, Cl, Br, I.
7. preparation method according to claim 2, it is characterized in that the carriers selected from silica of described heterogeneous catalyst, aluminum oxide, Thorotrast, titanium dioxide, silica-alumina, silicon carbide, illiteracy holder soil and their composition inorganic carrier.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7247202B1 (en) * | 1999-02-17 | 2007-07-24 | Protensive Limited | Process for the conversion of a fluid phase substrate by dynamic heterogeneous contact with a solid agent |
| CN101649012B (en) * | 2009-07-30 | 2011-06-29 | 浙江大学 | Catalyst system for ethylene polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7247202B1 (en) * | 1999-02-17 | 2007-07-24 | Protensive Limited | Process for the conversion of a fluid phase substrate by dynamic heterogeneous contact with a solid agent |
| CN101649012B (en) * | 2009-07-30 | 2011-06-29 | 浙江大学 | Catalyst system for ethylene polymerization |
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