CN103183749B - Method for preparing polymer - Google Patents
Method for preparing polymer Download PDFInfo
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- CN103183749B CN103183749B CN201110451972.9A CN201110451972A CN103183749B CN 103183749 B CN103183749 B CN 103183749B CN 201110451972 A CN201110451972 A CN 201110451972A CN 103183749 B CN103183749 B CN 103183749B
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- 238000000034 method Methods 0.000 title claims abstract description 55
- 229920000642 polymer Polymers 0.000 title abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 229920000098 polyolefin Polymers 0.000 claims description 40
- 239000000126 substance Substances 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 19
- 150000001336 alkenes Chemical class 0.000 claims description 16
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 239000012968 metallocene catalyst Substances 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 2
- -1 propylene, butylene, hexene Chemical class 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 8
- 239000007789 gas Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000036314 physical performance Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 208000011117 substance-related disease Diseases 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a method for preparing polymer; a polymerization temperature in a reactor is set to change circularly between a high temperature point and a lower temperature point; the cycle has at least one period within 6 hours; the high temperature point is higher than the low temperature point by more than 10 DEG C. Polymer prepared by the method of the invention has a ratio of flow index MI 21.6 to melt index MI 21.6 being more than 60, which indicates that the polymer has excellent processability; in addition, the polymer obtained in the invention has improved yield strength, breaking strength, and falling dart impact values when compared with the prior art, which indicates that the polymer has excellent physical properties.
Description
Technical field
The present invention relates to a kind of method preparing polymkeric substance, realize particular by the temperature of reaction controlling different time in reactor.
Background technology
As everyone knows, olefin polymer widespread use in each field, the rigidity that it has, toughness, Lightness be that many materials are not replaceable, improving Olefins is also the target that scientific research personnel constantly pursues.In the process of manufacture olefin polymer well known in the art, traditional polymerization process is in single reaction vessel, by Z-N, metallocene or chromium-based catalysts catalysis in olefine polymerization.In the process, control certain characteristic of polymkeric substance by the change of combining some polymerization parameter, thus realize the application of polymkeric substance in different field.No matter practice shows it is the olefin polymer material of which kind of purposes, all require that there is good physicals and processing characteristics, and what determine these performances is molecular size range and the molecular weight distribution of polymkeric substance.
The polymerization reaction parameter affecting molecular size range in single reaction vessel comprises: catalyst type, density of hydrogen, polymerization temperature, comonomer concentration, modifier concentration etc., these parameters are combined into different working method, to produce the polymkeric substance of certain specific end use by it to molecular weight effects degree difference.Such as, there is with the olefin polymer that Z-N or metallocene catalyst are produced the feature of narrow molecular weight distribution; And hydrogen has the greatest impact to polymericular weight size in operating parameters.By that analogy, when needing production to have the polymkeric substance of specific end use, after the molecular size range of target setting polymkeric substance, all polymerization reaction parameter optimizations affecting molecular size range are determined to become on respective steady state value the concrete operation method of industrial production olefin polymer.If in operation, some makes catalyzer reduce the material of active even inactivation (as O
2, CO, CO
2, H
2o etc.) existence when affecting the molecular size range of subject polymer, revise by the concentration changing hydrogen within the specific limits, thus continue the molecular weight of realize target polymkeric substance, thus hydrogen is also referred to as conditioning agent.This sole operation method adopted when being and producing the polymkeric substance of different purposes at present in single polymerization reactor.Because the olefin polymer produced with Z-N, metallocene catalyst has narrower molecular weight distribution, and existing working method can only control molecular size range and can not the distribution of Molecular regulator amount in single reaction vessel, by improving molecular weight as far as possible to increase the physicals of polymkeric substance under the prerequisite ensureing processing characteristics, the development and application of olefin polymer can only be thus limited concerning the polymkeric substance of certain purposes fixed.
In recent years, improve simultaneously to make the processing characteristics of olefin polymer and mechanical-physical and reach balance, a kind of method is the composite catalyst adopting both metallocene and Z-N to form in single reaction vessel, one of them catalysis produces low molecule and is beneficial to polymer processing performance, and another kind of catalysis produces polymer to improve polymer machinery physicals.But because different components in composite catalyst is different to the sensitivity of reaction conditions, be often difficult to the balance realizing sized molecules in olefin polymer, thus so far can not commercialized running.Another kind method selects single Ziegler-Natta catalyst catalytic production of olefins polymkeric substance in many tandem reactors, wherein improve in a reactor density of hydrogen produce molecular weight polymers and in another reactor not hydrogenation produce high polymer, realize sized molecules by this technological process method to mix by a certain percentage, to reach the object that processing characteristics and mechanical and physical performance improve simultaneously, but the shortcoming of this method to be technological process capital intensive, complicated operation, product cost huge.
The invention provides a kind of working method of the polymerization temperature of varying cyclically within a certain period of time, be surprised to find and use Ziegler-Natta catalyst or metallocene and metallocene composite catalyst in single polymerization reactor, namely can produce the very wide and olefin polymer containing ultra-high molecular weight of molecular weight distribution, namely the polymkeric substance produced has excellent processing characteristics and mechanical and physical performance simultaneously, and this is irrealizable with single polymerization reactor in prior art.
Summary of the invention
The invention provides a kind of method preparing polymkeric substance, comprise and the polymerization temperature in reactor is set to circulation change between high temperature dot and low warm spot, described in circulate in 6 hours and at least there is one-period, and described high temperature dot is higher than low warm spot more than 10 DEG C.
In high temperature dot and the temperature range close with high temperature dot, produce small molecules, and produce macromole in low warm spot and the temperature range close with low warm spot.
That is, polymerization temperature changes to low warm spot from high temperature dot or low warm spot or high temperature dot changes back to high temperature dot again or this circulating in 6 hours of low warm spot at least exists once in the present invention.High temperature dot described in preferred the present invention is be selected from the temperature spot in 60 ~ 150 DEG C, and described low warm spot is be selected from the temperature spot in 20 ~ 80 DEG C.Wherein preferred described high temperature dot is be selected from the temperature spot in 80 ~ 120 DEG C again, and low warm spot is be selected from the temperature spot in 40 ~ 75 DEG C; Preferred described high temperature dot is selected from 90 ~ 120 DEG C again, and low temperature point is selected from 50 ~ 70 DEG C; More preferably described high temperature dot is selected from 105 ~ 120 DEG C, and low temperature point is selected from 60 ~ 70 DEG C.
In other words, in the present invention, preferred described low warm spot is the 50% corresponding temperature of reaction with (as 70 ~ 90 DEG C) catalyst activity value under polyreaction optimum temperuture; Preferred described high temperature dot is the temperature of lower than the sticking temperature of olefin polymer 5 DEG C.
According to the specific embodiment of the present invention, circulate in 5 hours preferably and at least there is one-period, more preferably in 4 hours, at least there is one-period.In addition, polyreaction can keep 0 ~ 4 hour, preferably 0 ~ 2 hour, more preferably 0.5 ~ 1 hour under the temperature value of each high temperature dot and/or low warm spot.
The catalyzer selected in the present invention can be Ziegler-Natta catalyst well known in the art, inorganic chromium catalyzer, organic chromium catalyzer or metallocene catalyst, the composite catalyst of preferred Ziegler-Natta catalyst or metallocene and Z-N.Time in used catalyst of the present invention containing Ziegler-Natta catalyst, preferably carry out under promotor effect.Available promotor comprises: trimethyl aluminium, triethyl aluminum, aluminium isobutyl, a chlorine diethyl etc., preferred triethyl aluminum.
The technological process selected in the present invention can be arbitrary, and this comprises: what slurry process, body process, solution processes, gas phase process, preferred what slurry and gas phase process, more preferably gas phase process.Under gas phase process, olefin polymerization reactor can be gas phase annular tube type, bubble agitation autoclave, gas phase fluidization bed, preferably gas-phase fluidized-bed polymerizing reactor.In gas-phase fluidized-bed polymerizing reactor, preferred single reaction vessel.
The regulation and control of polymer property realize, as polymerization temperature height, comonomer concentration, modifier concentration in density of hydrogen, reactor in catalyst type, reaction mass by changing these parameters following in olefinic polyreaction process.In the present invention, the characteristic of purpose polymers jointly can be regulated and controled in conjunction with the mode of above-mentioned any one or many kinds of parameters and temperature circulation change between high temperature dot and low warm spot.
According to the present invention, in olefin polymerization reactor, polymeric reaction temperature refers to the temperature value of any part in reactor, preferably the bed temperature of regulation and control fluidized-bed reactor.More preferably detector unit is arranged at least 2mm, preferably 20mm, more preferably the 200mm depths, bed inside of fluidized-bed reactor radial direction; With agility, reflect real polymerization temperature exactly.
In the process of manufacture olefin polymer well known in the art, the working pressure of preferred gas-phase fluidized-bed polymerizing reactor is at 0.5 ~ 3.0Mpa, preferably 1.2 ~ 2.5Mpa.In circulation gas composition, concentration of olefin is at 1.0 ~ 60.0% (v/v), alkane concentration 0.1 ~ 20.0% (v/v), density of hydrogen 0.00 ~ 10.0% (v/v), inert gas concentration 1.0 ~ 50.0% (v/v).Described alkene comprises ethene, propylene, butylene, amylene, hexene, octene or higher alpha-olefin etc., and described alkane comprises ethane, propane, butane, pentane, hexane etc., and described rare gas element is nitrogen.Wherein, in the gas phase composition preferably in reactor, density of hydrogen is the some steady state values between 0.00 ~ 10.0% (v/v).In the present invention, the polymeric articles of the different trade mark needs different density of hydrogen, can select the polymkeric substance of production more than hundred different trades mark in above-mentioned density of hydrogen, and the density of hydrogen that the polymkeric substance of each trade mark needs is constant.
In a concrete olefin polymer preparation process, conversion unit forms an airtight circulation loop by gas-phase fluidized-bed reactor, recycle gas water cooler, circulating air compressor, catalyzer, alkene, alkane and rare gas element enter continuously bottom fluidized-bed reactor, and the olefin polymer prepared is discharged continuously from reactor.Unpolymerized material from reactor head out compressed and cooling after reenter fluidized-bed reactor.
Preferably make described recycle gas be compressed and cool rear generating portion liquid stream, this liquid stream can be used for cooling bed, thus controls the change of bed temperature in polymerization reactor.Preferred liquid logistics capacity accounts for 10 ~ 50wt% of recycle gas, is more preferably 20 ~ 30wt%.
Preferably luxuriant-Qi composite catalyst or Qi-Qi composite catalyst is used in fluidized-bed polymerization reactor; Its preparation method can refer to patent application WO2008/116396A1.This catalyzer injects in the bed of fluidized-bed reactor continuously or discontinuously, be select low warm spot bet into catalyzer and keep this low temperature point operation 0 ~ 4 hour, preferably 0 ~ 2 hour, more preferably 0.5 ~ 1 hour stop add catalyzer, namely be warmed up to high temperature dot when the bed temperature of fluidized-bed polymerization reactor remains on low warm spot immediately after 0.5 ~ 1 hour, stablize under high temperature dot 0 ~ 4 hour, cool to rapidly low warm spot behind preferably 0 ~ 2 hour, more preferably 0.5 ~ 1 hour.According to the present invention, the temperature changing speed between each high temperature dot and low warm spot is 0.1 ~ 8 DEG C/min, preferably 1 ~ 6 DEG C/min, more preferably 2 ~ 5 DEG C/min.
Easy understand, the modulation of control mild temperature realizes by outside temperature controller.
According to the present invention, the bed volume of olefinic polymerization fluidized-bed reactor is also revocable, described bed volume by with olefin polymer for the main volume formed, described volume increases with olefinic polymerization heighten degree or reduces with olefin polymer discharging current fluidized bed reactor.
In order to make those skilled in the art more understand the present invention, by Fig. 1 and Fig. 2 temperature operation mode feasible in the present invention being made and further illustrating.Change to high temperature dot from low warm spot to change back to this cyclical operation of low warm spot more consuming time for 3.33h at every turn in FIG.In FIG, ordinate zou is the bed temperature of fluidized-bed polymerization reactor, and X-coordinate is time schedule.A point is low warm spot, its ordinate zou is 60 DEG C (in corresponding diagram 20% places), X-coordinate is 0min, add catalyzer at A point to reactor and start reaction, maintain 40min to B point at this temperature, then with the speed ascending fluidization bed temperature of 1 DEG C/min to high temperature dot C point, its ordinate zou is 120 DEG C (in corresponding diagram 100% places), and X-coordinate is 100min, and keeping high temperature dot 40min to D point, D point X-coordinate is 140min; Then reduce fluidized-bed layer temperature to 60 DEG C of E point by 1 DEG C/min speed, its X-coordinate is 200min, i.e. 3.33h.Maintain temperature 40min to the F point of E point, the time that F point is corresponding is 240min, i.e. 4h, enters another circulation of temperature from E point.
In this embodiment corresponding with Fig. 1, in AB section and EF section, namely then stop adding catalyzer whenever temperature retention value 2 DEG C higher than 60 DEG C of the bed temperature of fluidized-bed polymerization reactor, therefore in this operating method, catalyzer adds reactor in intermittent cycle mode.In the present invention, reach when the bed temperature of described fluidized-bed polymerization reactor and maintain after high temperature dot arrives D point, when the intersegmental temperature of DE is reduced in 0 ~ 5 DEG C, also be after D point in 0 ~ 5min, olefin polymer starts to discharge continuously until stop discharging when the bed temperature of described fluidized-bed polymerization reactor is reduced to lower-most point E from reactor.According to present embodiment, olefin polymer is discharged from fluidized-bed reactor in intermittent cycle mode.
And change to high temperature dot from low warm spot to change back to this cyclical operation of low warm spot more consuming time for 1h at every turn in fig. 2, namely can carry out four this cyclical operations in 4h.G point is low warm spot, its ordinate zou is 60 DEG C (in corresponding diagram 20% places), X-coordinate is 0:00min, in reactor, add catalyzer at G point and start polymer reaction, just with the speed of 2 DEG C/min, fluidized-bed layer temperature is raised to high temperature dot H point when polyreaction heat release makes bed temperature raise 1 ~ 2 DEG C, its ordinate zou is 120 DEG C (in corresponding diagram 100% places), and X-coordinate is 30min; And then reduce fluidized-bed layer temperature to low warm spot I point by the speed of 2 DEG C/min, its ordinate zou is 60 DEG C, X-coordinate is 60min.
In the embodiment that Fig. 2 is corresponding, catalyzer adds reactor with intermittent type or continuous circulation mode; Equally, olefin polymer is discharged from fluidized-bed reactor with intermittent type or continuous circulation mode.
According to the inventive method, the olefin polymer made under low warm spot has larger molecular weight, its MI
2.16be less than 0.1g/10min, be preferably less than 0.05g/10min, its density is less than 0.930g/cm
3, be preferably less than 0.920g/cm
3; And the olefin polymer made under high temperature dot has less molecular weight, its MI
2.16be greater than 0.5g/10min, be preferably greater than 1.0g/min, more preferably greater than 2.0g/10min, its density is greater than 0.930g/cm
3.
The polymkeric substance melt flow ratio MFR using the inventive method to prepare and flow index MI
21.6with melt index MI
2.16ratio be greater than 60.
Accompanying drawing explanation
Fig. 1 is the temperature-controlled process figure preparing polymkeric substance in one embodiment of the present invention;
Fig. 2 is the temperature-controlled process figure preparing polymkeric substance in another embodiment of the invention;
Fig. 3 is the performance chart of the polymkeric substance prepared in the embodiment of the present invention 1
Embodiment
Weight of otefi pi polymer size melt index MI
2.16characterize.Term " melt index " is the melt flow rate (MFR) measured according to the GB/T-3682-2000 condition load of 2.16kg (190 DEG C).
Weight of otefi pi polymer Tile Width melt flow ratio MFR characterizes.Term " melt flow ratio " refers to MI
21.6with MI
2.16ratio, i.e. the ratio of " flow index " and " melt index ".Wherein, term " flow index " is the melt flow rate (MFR) measured according to the GB/T-3682-2000 condition load of 21.6kg (190 DEG C).The unit of melt index and flow index is g/10min, and therefore, the melt flow ratio MFR of characterize polymers molecular weight distribution width is the numerical value without the factor.
The density of olefin polymer measures according to GB/1033-1986 method.
Dart drop value is according to the method A test in GB/T9639.1-2008.
The tensile strength of polymkeric substance uses the method for GB/T1040.1 to measure.
In embodiments of the present invention, yield strength, breaking tenacity and dart drop value is adopted to characterize the physicals of olefin polymer.The molecular weight distribution that employing melt flow ratio MFR represents is to characterize the processing characteristics of olefin polymer.
Embodiment 1
Catalyst preparing: introduce method for preparing catalyst in patent application WO2008/116396A1 and prepare catalyzer in the present embodiment.The first step prepares Ziegler-Natta catalyst (ZN) by Mg/Ti=5: 1; mould material is carried on described Ziegler-Natta catalyst by second step; 3rd step is by MMAO (modified methylaluminoxane) and butyl two luxuriant dichloro zirconium mixing back loading on described rete, and the 4th step is by stand-by except storing under desolventizing, nitrogen protection for described composite catalyst drying.
Prepared by polymkeric substance: a diameter be 3 meters, in the industrial fluidized bed olefin polymerization reactor of straight tube height 12 meters, adding inert nitrogen gas makes reactor pressure reach 5.0Mpa, start the compressor in cycling element, and with the nitrogen of interchanger heating cycle, fluidized-bed bed temperature raised and controls at 120 DEG C, moisture in fluidized-bed reactor is displaced, until water-content is less than 10ppm to make hot nitrogen.
In reactor, add triethyl aluminum 50ppm, circulate 4 hours until moisture is 0.00ppm in reactor.In reactor, add ethene, butylene and iso-pentane successively in proportion, circulation gas in cycling element is consisted of: ethene 48.33%v/v, butylene 2.65%v/v, iso-pentane 10.20%v/v, ethane 0.08%v/v, butane 0.03%v/v, nitrogen 38.71%v/v.Now bed temperature in fluidized-bed reduced and be stabilized in 60 DEG C, this is the low warm spot in the present embodiment.In reactor, add promotor triethyl aluminum 300ppm, then start catalyzer feeding equipment and the catalyzer prepared as stated above is added reactor with the flow rate of 1.0kg/hr, polyreaction starts and starts timing.First making in fluidized-bed reactor temperature-stable at 60 ± 2 DEG C and maintain 1 hour, the concentration of alkene in circulation gas controls constant during this period.Concrete temperature actuated method is: when reactor internal olefin polymerization exotherm makes bed temperature rising reach 2 DEG C, stop immediately adding catalyzer to reactor.Then bed temperature be elevated to 118 ± 2 DEG C with the speed of 2 DEG C/min and maintain 1 hour, this is the high temperature dot in the present embodiment.Then with the speed of 2 DEG C/min, bed temperature is dropped to 60 DEG C.Between this cooldown period, start reactor discharge system olefin polymer is discharged reactor automatically, it is 12000kg/hr that olefin polymer on average prepares speed.From reactor discharge olefin polymer at degassed 400m
3the hydrocarbon compound of removing unreacted polymerization in container, until its content is less than 100ppm, take out olefin polymer, its related property data list in table 1.The physical data of the respective films product using this olefin polymer to prepare also lists in table 1.
Embodiment 2
Catalyst preparing: introduce method for preparing catalyst in patent application WO2008/116396A1 and prepare catalyzer in the present embodiment.The first step prepares Ziegler-Natta catalyst (ZN-1) by Mg/Ti=5: 1; mould material is carried on described ZN-1 by second step; another kind of Ziegler-Natta catalyst (ZN-2) is carried on described rete by the 3rd step, and the 4th step is by stand-by except storing under desolventizing, nitrogen protection for described catalyzer drying.
Prepared by polymkeric substance: a diameter be 3 meters, in the industrial fluidized bed olefin polymerization reactor of straight tube height 12 meters, adding inert nitrogen gas makes reactor pressure reach 5.0Mpa, start the compressor in cycling element, and with the nitrogen of interchanger heating cycle, fluidized-bed bed temperature raised and controls at 103 DEG C, moisture in fluidized-bed reactor is displaced, until water-content is less than 10ppm to make hot nitrogen.In reactor, add triethyl aluminum 50ppm, circulate 4 hours until moisture is 0.00ppm in reactor.In reactor, add ethene, butylene and iso-pentane successively in proportion, circulation gas in cycling element is consisted of: ethene 38.91%v/v, butylene 10.05%v/v, iso-pentane 7.20%v/v, ethane 0.02%v/v, butane 0.03%v/v, nitrogen 43.79%v/v.Now bed temperature in fluidized-bed reduced and be stabilized in 70 DEG C, this is the low warm spot in the present embodiment.
In reactor, add promotor triethyl aluminum 350ppm, then start catalyzer feeding equipment and the catalyzer prepared as stated above is added reactor with the flow rate of 1.0kg/hr, polyreaction starts and starts timing.First making in fluidized-bed reactor temperature-stable at 70 ± 2 DEG C and maintain 1 hour, the concentration of alkene in circulation gas controls constant during this period.Concrete temperature actuated method is: when reactor internal olefin polymerization exotherm makes bed temperature rising reach 2 DEG C, stop immediately adding catalyzer to reactor.Then bed temperature be elevated to 103 ± 2 DEG C with the speed of 2 DEG C/min and maintain 1 hour, this is the high temperature dot in the present embodiment.Then with the speed of 2 DEG C/min, bed temperature is dropped to 70 DEG C.Between this cooldown period, start reactor discharge system olefin polymer is discharged reactor automatically, it is 16000kg/hr that olefin polymer on average prepares speed.From reactor discharge olefin polymer at degassed 400m
3the hydrocarbon compound of removing unreacted polymerization in container, until its content is less than 100ppm, take out olefin polymer, its related property data list in table 1.The physical data of the respective films product using this olefin polymer to prepare also lists in table 1.
Comparative example 1
Carry out Molecular regulator amount with use temperature in embodiment 1 to vary in size, comparative example 1 middle-molecular-weihydroxyethyl size uses hydrogen to regulate.
Catalyst preparing and polymer preparation process substantially the same manner as Example 1, difference is the bed temperature not circulation change between low warm spot and high temperature dot of fluidized-bed polymerization reactor, but temperature of reaction controls at 80 ± 3 DEG C in whole polymerization process, regulate the molecular size range of olefin polymer with hydrogen, in circulation gas, density of hydrogen changes between 200 ~ 1000ppm (i.e. 0.02 ~ 0.1%v/v).
Comparative example 2
Carry out Molecular regulator amount with use temperature in embodiment 2 to vary in size, comparative example 2 middle-molecular-weihydroxyethyl size uses hydrogen to regulate.
Catalyst preparing and polymer preparation process substantially the same manner as Example 2, difference is the bed temperature not circulation change between low warm spot and high temperature dot of fluidized-bed polymerization reactor, but temperature of reaction controls at 87 ± 3 DEG C in whole polymerization process, regulate the molecular size range of olefin polymer with hydrogen, in circulation gas, density of hydrogen changes between 1.03 ~ 5.38%v/v.
Table 1
Yield strength, breaking tenacity and dart drop value as can be seen from table 1, use the physicals of the respective films product that olefin polymer prepares in the inventive method embodiment 1 and 2 to be obviously better than the physicals of comparative example respective films product.
In distribution plan polymer property analysis obtained with gel chromatograph (GPC), 10
6the weight-average molecular weight M of level
whave and significantly increase or conditions of streaking, the ultra-high molecular weight part shown in figure substantially increases the physicals of olefin polymer.The M of phase emergencing copolymer in Fig. 3
n=2.3 × 10
4; M
w=2.97 × 10
5; M
z=1.86 × 10
6; M
z+1=4.04 × 10
6.
Melt flow ratio MFR value as can be seen from table 1, in embodiment, the processing characteristics of olefin polymer is obviously better than the processing characteristics of phase emergencing copolymer in comparative example.
Claims (14)
1. utilize reactor to prepare a method for polymkeric substance, comprise and the polymerization temperature in reactor is set to circulation change between high temperature dot and low warm spot, described in circulate in 6 hours and at least there is one-period, and described high temperature dot is higher than low warm spot more than 10 DEG C; Temperature changing speed between each high temperature dot and low warm spot is 0.1 ~ 8 DEG C/min; Described high temperature dot is be selected from the temperature spot in 60 ~ 150 DEG C, and described low warm spot is be selected from the temperature spot in 20 ~ 80 DEG C; Use alkene homopolymerization or copolymerization to prepare described polymkeric substance, wherein alkene is selected from one or more in ethene, propylene, butylene, hexene, amylene, octene; Catalyzer, alkene, alkane and rare gas element enter continuously bottom gas-phase fluidized-bed reactor, and the olefin polymer prepared is discharged continuously from reactor.
2. method according to claim 1, is characterized in that: described high temperature dot is be selected from the temperature spot in 80 ~ 120 DEG C, and low warm spot is be selected from the temperature spot in 40 ~ 75 DEG C.
3. method according to claim 2, is characterized in that: described high temperature dot is selected from 90 ~ 120 DEG C, and low temperature point is selected from 50 ~ 70 DEG C.
4. method according to claim 2, is characterized in that: described high temperature dot is selected from 105 ~ 120 DEG C, and low temperature point is selected from 60 ~ 70 DEG C.
5. method according to claim 1, is characterized in that: described in circulate in 5 hours and at least there is one-period.
6. method according to claim 5, is characterized in that: described in circulate in 4 hours and at least there is one-period.
7. method according to claim 1, is characterized in that: polyreaction keeps 0 ~ 4 hour under the temperature value of each high temperature dot and/or low warm spot.
8. method according to claim 7, is characterized in that: polyreaction keeps 0 ~ 2 hour under the temperature value of each high temperature dot and/or low warm spot.
9. method according to claim 7, is characterized in that: polyreaction keeps 0.5 ~ 1 hour under the temperature value of each high temperature dot and/or low warm spot.
10. method according to claim 1, is characterized in that: the temperature changing speed between each high temperature dot and low warm spot is 1 ~ 6 DEG C/min.
11. methods according to claim 10, is characterized in that: the temperature changing speed between each high temperature dot and low warm spot is 2 ~ 5 DEG C/min.
12. methods according to claim 1, is characterized in that: preparing polymkeric substance catalyzer used is one or more in Ziegler-Natta catalyst, metallocene catalyst, Z-N and metallocene composite catalyst.
13., according to method described in claim 12, is characterized in that: use triethyl aluminum to be promotor when preparing polymkeric substance.
14. methods according to claim 1, is characterized in that: the melt flow ratio MFR of described polymkeric substance and flow index MI
21.6with melt index MI
2.16ratio be greater than 60.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2001077193A1 (en) * | 2000-04-10 | 2001-10-18 | Bp Chemicals Limited | Polymerisation process |
| US6753387B1 (en) * | 2003-03-19 | 2004-06-22 | Chevron Phillips Chemical Company Lp | Temperature controlling system for olefin polymerization reactors |
| CN1939938A (en) * | 2005-09-29 | 2007-04-04 | 中国石油化工股份有限公司 | Propylene polymerization or copolymerization and its multipolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001077193A1 (en) * | 2000-04-10 | 2001-10-18 | Bp Chemicals Limited | Polymerisation process |
| US6753387B1 (en) * | 2003-03-19 | 2004-06-22 | Chevron Phillips Chemical Company Lp | Temperature controlling system for olefin polymerization reactors |
| CN1939938A (en) * | 2005-09-29 | 2007-04-04 | 中国石油化工股份有限公司 | Propylene polymerization or copolymerization and its multipolymer |
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