CN103183749A - Method for preparing polymer - Google Patents
Method for preparing polymer Download PDFInfo
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- CN103183749A CN103183749A CN2011104519729A CN201110451972A CN103183749A CN 103183749 A CN103183749 A CN 103183749A CN 2011104519729 A CN2011104519729 A CN 2011104519729A CN 201110451972 A CN201110451972 A CN 201110451972A CN 103183749 A CN103183749 A CN 103183749A
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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 for preparing polymkeric substance, specifically is to realize by the temperature of reaction of controlling different time in the reactor.
Background technology
As everyone knows, olefin polymer widespread use in each field, the rigidity that it has, toughness, lightweight are that many materials can not replace, improving and improving the alkene performance also is the target that the scientific research personnel constantly pursues.In the process of manufacturing 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 this process, control the polymkeric substance specific character by the variation that some polymerization parameter are made up, thereby 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 to have good physicals and processing characteristics, and what determine these performances is molecular weight size and the molecular weight distribution of polymkeric substance.
The polymerization reaction parameter that influences the molecular weight size 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 by it to molecular weight influence degree difference, to produce the polymkeric substance of certain specific end use.Such as, have the characteristics of narrow molecular weight distribution with the olefin polymer of Z-N or metallocene catalyst production; And hydrogen has the greatest impact to the polymericular weight size in the operating parameters.By that analogy, when needs production has the polymkeric substance of specific end use, after the molecular weight size of target setting polymkeric substance, all polymerization reaction parameter optimizations that influence the molecular weight size are determined to become at steady state value separately the concrete operation method of industrial production olefin polymer.If in operating process, some makes catalyzer reduce the material of activity even inactivation (as O
2, CO, CO
2, H
2When existence O etc.) influences the molecular weight size of subject polymer, can revise by the concentration that changes hydrogen within the specific limits, thereby continuation realizes the molecular weight of subject polymer, thereby hydrogen is also referred to as conditioning agent.This is the unique working method that adopts when producing the polymkeric substance of different purposes at present in single polymerization reactor.Because the olefin polymer with Z-N, metallocene catalyst production has narrower molecular weight distribution, and existing working method can only be controlled molecular weight size and can not regulate the distribution of molecular weight in the single reaction vessel, concerning the polymkeric substance of fixed certain purposes, can only guarantee under the prerequisite of processing characteristics by improving molecular weight as far as possible increasing the physicals of polymkeric substance, thereby limit the development and application of olefin polymer.
In recent years, for the processing characteristics that makes olefin polymer and mechanical-physical improve simultaneously and reach balance, a kind of method is to adopt the composite catalyst of metallocene and the two composition of Z-N in single reaction vessel, one of them catalysis produces low molecule and is beneficial to the polymer processing performance, and another kind of catalysis produces polymer to improve the polymer machinery physicals.But because of the sensitivity difference of different components in the composite catalyst to reaction conditions, often be difficult to realize the balance of sized molecules in the olefin polymer, thereby so far can not commercialized running.Another kind method is to select single Ziegler-Natta catalyst catalytic production of olefins polymkeric substance in many tandem reactors for use, wherein improving density of hydrogen in a reactor produces the small molecules polymkeric substance and do not add hydrogen generation high polymer in another reactor, mix by a certain percentage with this technological process method realization sized molecules, reaching the purpose that processing characteristics and mechanical and physical performance improve simultaneously, but that the shortcoming of this method is technological process investment costliness, complicated operation, product cost is 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 that to use Ziegler-Natta catalyst or metallocene and metallocene composite catalyst namely can produce molecular weight distribution in single polymerization reactor very wide and contain the olefin polymer of ultra-high molecular weight, namely the polymkeric substance of Sheng Chaning has good processing characteristics and mechanical and physical performance simultaneously, and this is irrealizable with single polymerization reactor in the prior art.
Summary of the invention
The invention provides a kind of method for preparing polymkeric substance, comprise that the polymerization temperature in the reactor is set to circulation change between high temperature dot and low warm spot, there is one-period at least in described circulating in 6 hours, and described high temperature dot is higher more than 10 ℃ than low warm spot.
Produce small molecules in the temperature range that approaches at high temperature dot and with high temperature dot, and produce macromole at low warm spot and with hanging down in the temperature range that warm spot approaches.
That is to say that polymerization temperature changes to low warm spot or high temperature dot changes back to high temperature dot again or this circulating in 6 hours of low warm spot exists once at least from high temperature dot or low warm spot in the present invention.High temperature dot is the temperature spot that is selected from 60～150 ℃ described in preferred the present invention, and described low warm spot is the temperature spot that is selected from 20～80 ℃.Wherein preferred described high temperature dot is the temperature spot that is selected from 80～120 ℃ again, and low warm spot is the temperature spot that is selected from 40～75 ℃; Preferred described high temperature dot is selected from 90～120 ℃ again, and the low temperature point is selected from 50～70 ℃; More preferably described high temperature dot is selected from 105～120 ℃, and the low temperature point is selected from 60～70 ℃.
In other words, among the present invention preferred described low warm spot be with the polyreaction optimum temperuture under the 50% corresponding temperature of reaction of (as 70～90 ℃) catalyst activity value; Preferred described high temperature dot is the temperature than low 5 ℃ of the sticking temperature of olefin polymer.
According to the specific embodiment of the present invention, there is one-period at least in preferred described circulating in 5 hours, more preferably had one-period in 4 hours at least.In addition, polyreaction can keep under the temperature value of each high temperature dot and/or low warm spot 0～4 hour, and preferred 0～2 hour, more preferably 0.5～1 hour.
The catalyzer of selecting among 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.When containing Ziegler-Natta catalyst in the catalyst system therefor of the present invention, preferably under the promotor effect, carry out.Available promotor comprises: trimethyl aluminium, triethyl aluminum, aluminium isobutyl, a chlorine diethyl etc., preferred triethyl aluminum.
The technological process of selecting among the present invention can be that this comprises arbitrarily: what slurry process, body process, solution process, gas phase process, preferred what slurry and gas phase process, more preferably gas phase process.Under the gas phase process process, olefin polymerization reactor can be gas phase annular tube type, gas phase stirring tank formula, gas-phase fluidized-bed formula, preferably gas-phase fluidized-bed polymerizing reactor.In gas-phase fluidized-bed polymerizing reactor, preferred single reaction vessel.
Following these parameters realize in the olefinic polyreaction process by changing in the regulation and control of polymer property, as polymerization temperature height, comonomer concentration, modifier concentration in density of hydrogen, the reactor in catalyst type, the reaction mass.In the present invention, can regulate and control the characteristic of purpose polymers in conjunction with the mode of above-mentioned any one or multiple parameter and temperature circulation change between high temperature dot and low warm spot jointly.
According to the present invention, polymeric reaction temperature refers to the temperature value of any part in the reactor in the olefin polymerization reactor, preferably regulates and control the bed temperature of fluidized-bed reactor.More preferably detector unit is installed in fluidized-bed reactor bed inside radially 2mm, preferred 20mm, more preferably 200mm depths at least; With quick, reflect real polymerization temperature exactly.
In the process of manufacturing olefin polymer well known in the art, the working pressure of preferred gas-phase fluidized-bed polymerizing reactor is at 0.5～3.0Mpa, preferred 1.2～2.5Mpa.Concentration of olefin was 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) during circulation gas was formed.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, density of hydrogen was the some steady state values between 0.00～10.0% (v/v) during preferably the gas phase in reactor was formed.In the present invention, the polymeric articles of the different trades mark needs different density of hydrogen, can select to produce the polymkeric substance of more than hundred the 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 is formed 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 from the fluidized-bed reactor bottom continuously, and the olefin polymer for preparing is discharged from reactor continuously.Unpolymerized material from reactor head come out compressed and the cooling after reenter fluidized-bed reactor.
Make that preferably described recycle gas is compressed and cool off the logistics of back generation partially liq, this liquid stream can be used for cooling off bed, thus the variation of bed temperature in the control polymerization reactor.The preferred liquid logistics capacity accounts for 10～50wt% of recycle gas, more preferably 20～30wt%.
Preferred luxuriant-Qi composite catalyst or the Qi-Qi composite catalyst of using in the fluidized-bed polymerization reactor; Its preparation method can be with reference to patent application WO2008/116396A1.This catalyzer injects in the bed of fluidized-bed reactor continuously or discontinuously, be the low warm spot of selecting make a bet into catalyzer and keep this low temperature point operation 0～4 hour, preferred 0～2 hour, more preferably stopped to add catalyzer in 0.5～1 hour, namely be warmed up to high temperature dot after 0.5～1 hour immediately when the bed temperature of fluidized-bed polymerization reactor remains on low warm spot, under high temperature dot, stablize 0～4 hour, preferred 0～2 hour, more preferably cool to low warm spot rapidly after 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 ℃/min, preferred 1～6 ℃/min, 2～5 ℃/min more preferably.
Understand easily, the modulation of temperature control and temperature can be realized by outside temperature controller.
According to the present invention, the bed volume of olefinic polymerization fluidized-bed reactor is also revocable, described bed volume is by being a main volume of forming with the olefin polymer, and described volume increases with the olefinic polymerization heighten degree or reduces with olefin polymer discharging current fluidized bed reactor.
In order to make those skilled in the art understand the present invention more, make by feasible temperature operation mode among Fig. 1 and the present invention of Fig. 2 and to further specify.In Fig. 1, change to high temperature dot from low warm spot at every turn and change back to low this cyclical operation of the warm spot 3.33h of being consuming time again.In Fig. 1, ordinate zou is the bed temperature of fluidized-bed polymerization reactor, and X-coordinate is time schedule.The A point is low warm spot, its ordinate zou is that 60 ℃ of (20% place in the corresponding diagram), X-coordinates are 0min, add catalyzer at the A point to reactor and begin reaction, under this temperature, keep 40min to the B point, speed rising fluidized-bed layer temperature with 1 ℃/min arrives high temperature dot C point then, and its ordinate zou is 120 ℃ (100% places in the corresponding diagram), and X-coordinate is 100min, and keep high temperature dot 40min to the D point, D point X-coordinate is 140min; Reduce the fluidized-bed layer temperature by 1 ℃/min speed then and arrive 60 ℃ that E is ordered, its X-coordinate is 200min, i.e. 3.33h.Keep temperature 40min to the F point that E is ordered, F point time corresponding is 240min, and namely 4h has begun to enter another circulation of temperature from the E point.
In this embodiment corresponding with Fig. 1, in AB section and EF section, namely then stop to add catalyzer when the bed temperature of fluidized-bed polymerization reactor is higher than 60 ℃ 2 ℃ of temperature retention values, therefore catalyzer adds reactor in the intermittent cycle mode in this operating method.In the present invention, after the bed temperature of described fluidized-bed polymerization reactor reaches and keeps high temperature dot and arrive the D point, when the intersegmental temperature of DE is reduced in 0～5 ℃, also be in the 0～5min of D point back, olefin polymer begins to stop to discharge when the bed temperature when described fluidized-bed polymerization reactor is reduced to lower-most point E from continuous discharge of reactor.According to present embodiment, olefin polymer is discharged from fluidized-bed reactor in the intermittent cycle mode.
Change back to low this cyclical operation of the warm spot 1h of being consuming time again and in Fig. 2, change to high temperature dot from low warm spot at every turn, namely in 4h, can carry out four this cyclical operations.The G point is low warm spot, its ordinate zou is that 60 ℃ of (20% place in the corresponding diagram), X-coordinates are 0:00min, add catalyzer in the reactor at the G point and begin polymer reaction, raise 1～2 ℃ the time just by bed temperature the speed with 2 ℃/min is raised to high temperature dot H point with the fluidized-bed layer temperature when the polyreaction heat release makes, its ordinate zou is 120 ℃ (100% places in the corresponding diagram), and X-coordinate is 30min; And then reduce the fluidized-bed layer temperature to low warm spot I point by the speed of 2 ℃/min, its ordinate zou is that 60 ℃, X-coordinate are 60min.
In the embodiment of Fig. 2 correspondence, catalyzer adds reactor with intermittent type or continous way Recycle design; Equally, olefin polymer is discharged from fluidized-bed reactor with intermittent type or continous way Recycle design.
According to the inventive method, the olefin polymer of making under low warm spot has bigger molecular weight, its MI
2.16Less than 0.1g/10min, preferably less than 0.05g/10min, its density is less than 0.930g/cm
3, preferably less than 0.920g/cm
3And the olefin polymer of making under high temperature dot has less molecular weight, its MI
2.16Greater 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 that uses the inventive method to prepare is flow index MI
21.6With melt index MI
2.16Ratio greater than 60.
Description of drawings
Fig. 1 is the temperature-controlled process figure of preparation polymkeric substance in one embodiment of the present invention;
Fig. 2 is the temperature-controlled process figure of preparation polymkeric substance in the another embodiment of the invention;
Fig. 3 is the performance chart of the polymkeric substance for preparing in the embodiment of the invention 1
Embodiment
Weight of otefi pi polymer size melt index MI
2.16Characterize.Term " melt index " is the melt flow rate (MFR) of measuring according to GB/T-3682-2000 condition (190 ℃, 2.16kg load).
The weight of otefi pi polymer Tile Width characterizes with melt flow ratio MFR.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) of measuring according to GB/T-3682-2000 condition (190 ℃, 21.6kg load).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 of the no factor.
The density of olefin polymer is measured according to the GB/1033-1986 method.
The dart impact value is tested according to the method A among the 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, adopt yield strength, breaking tenacity and dart impact value to characterize the physicals of olefin polymer.The molecular weight distribution that adopts melt flow ratio MFR to represent characterizes the processing characteristics of olefin polymer.
Preparation of Catalyst: method for preparing catalyst prepares catalyzer in the present embodiment among the introducing patent application WO2008/116396A1.The first step is pressed Mg/Ti=5: 1 preparation Ziegler-Natta catalyst (ZN); second step was carried on mould material on the described Ziegler-Natta catalyst; the 3rd step, on described rete, the 4th step was stand-by with storage under the desolventizing of described composite catalyst drying, the nitrogen protection with MMAO (modified methylaluminoxane) and butyl two luxuriant dichloro zirconium mixings back loadings.
Polymer manufacture: be in the industrial fluidized bed olefin polymerization reactor of 12 meters of 3 meters, straight tube height at a diameter, adding inert nitrogen gas makes reactor pressure reach 5.0Mpa, start the compressor in the cycling element, and raise with the nitrogen of interchanger heating cycle, with fluidized-bed bed temperature and control at 120 ℃, so that hot nitrogen displaces the moisture in the fluidized-bed reactor, up to water-content less than 10ppm.
Add triethyl aluminum 50ppm in the reactor, circulate 4 hours in reactor moisture be 0.00ppm.In reactor, add ethene, butylene and iso-pentane in proportion successively, make that circulation gas consists of in the cycling element: 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.Reduce bed temperature in the fluidized-bed and be stabilized in 60 ℃ this moment, and this is the low warm spot in the present embodiment.Add promotor triethyl aluminum 300ppm in the reactor, then start catalyzer that the catalyzer feeding equipment will prepare as stated above and add reactor with the flow rate of 1.0kg/hr, polyreaction begins and picks up counting.At first make in the fluidized-bed reactor temperature-stable at 60 ± 2 ℃ and kept 1 hour, the concentration control of alkene in circulation gas is constant during this period.Concrete temperature actuated method is: when reactor internal olefin polymerization exotherm makes the bed temperature rising reach 2 ℃, stop immediately adding catalyzer to reactor.Then bed temperature is elevated to 118 ± 2 ℃ and kept 1 hour with the speed of 2 ℃/min, this is the high temperature dot in the present embodiment.Then the speed with 2 ℃/min drops to 60 ℃ to bed temperature.Start the reactor discharge system between this cooldown period olefin polymer is discharged reactor automatically, it is 12000kg/hr that olefin polymer on average prepares speed.The 400m that the olefin polymer of discharging from reactor is outgasing
3Remove the hydrocarbon compound of unreacted polymerization in the container, less than 100ppm, take out olefin polymer up to its content, its relevant rerum natura data rows is in table 1.Use the physical data of the respective films product that this olefin polymer prepares also to list in table 1.
Preparation of Catalyst: method for preparing catalyst prepares catalyzer in the present embodiment among the introducing patent application WO2008/116396A1.The first step is pressed Mg/Ti=5: 1 preparation Ziegler-Natta catalyst (ZN-1); second step was carried on mould material on the described ZN-1; the 3rd step was carried on another kind of Ziegler-Natta catalyst (ZN-2) on the described rete, and the 4th step is stand-by with storing under the dry desolventizing of described catalyzer, the nitrogen protection.
Polymer manufacture: be in the industrial fluidized bed olefin polymerization reactor of 12 meters of 3 meters, straight tube height at a diameter, adding inert nitrogen gas makes reactor pressure reach 5.0Mpa, start the compressor in the cycling element, and raise with the nitrogen of interchanger heating cycle, with fluidized-bed bed temperature and control at 103 ℃, so that hot nitrogen displaces the moisture in the fluidized-bed reactor, up to water-content less than 10ppm.Add triethyl aluminum 50ppm in the reactor, circulate 4 hours in reactor moisture be 0.00ppm.In reactor, add ethene, butylene and iso-pentane in proportion successively, make that circulation gas consists of in the cycling element: 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.Reduce bed temperature in the fluidized-bed and be stabilized in 70 ℃ this moment, and this is the low warm spot in the present embodiment.
Add promotor triethyl aluminum 350ppm in the reactor, then start catalyzer that the catalyzer feeding equipment will prepare as stated above and add reactor with the flow rate of 1.0kg/hr, polyreaction begins and picks up counting.At first make in the fluidized-bed reactor temperature-stable at 70 ± 2 ℃ and kept 1 hour, the concentration control of alkene in circulation gas is constant during this period.Concrete temperature actuated method is: when reactor internal olefin polymerization exotherm makes the bed temperature rising reach 2 ℃, stop immediately adding catalyzer to reactor.Then bed temperature is elevated to 103 ± 2 ℃ and kept 1 hour with the speed of 2 ℃/min, this is the high temperature dot in the present embodiment.Then the speed with 2 ℃/min drops to 70 ℃ to bed temperature.Start the reactor discharge system between this cooldown period olefin polymer is discharged reactor automatically, it is 16000kg/hr that olefin polymer on average prepares speed.The 400m that the olefin polymer of discharging from reactor is outgasing
3Remove the hydrocarbon compound of unreacted polymerization in the container, less than 100ppm, take out olefin polymer up to its content, its relevant rerum natura data rows is in table 1.Use the physical data of the respective films product that this olefin polymer prepares also to list in table 1.
Comparative Examples 1
What regulate that molecular weight varies in size with use temperature among the embodiment 1 is that the molecular weight size is to use hydrogen to regulate in the Comparative Examples 1.
Preparation of Catalyst and polymer manufacture process are substantially the same manner as Example 1, difference is the bed temperature circulation change between low warm spot and high temperature dot not of fluidized-bed polymerization reactor, but temperature of reaction is controlled at 80 ± 3 ℃ in whole polymerization process, with the molecular weight size that hydrogen is regulated olefin polymer, density of hydrogen (namely changes between 0.02～0.1%v/v) at 200～1000ppm in the circulation gas.
Comparative Examples 2
What regulate that molecular weight varies in size with use temperature among the embodiment 2 is that the molecular weight size is to use hydrogen to regulate in the Comparative Examples 2.
Preparation of Catalyst and polymer manufacture process are substantially the same manner as Example 2, difference is the bed temperature circulation change between low warm spot and high temperature dot not of fluidized-bed polymerization reactor, but temperature of reaction is controlled at 87 ± 3 ℃ in whole polymerization process, with the molecular weight size that hydrogen is regulated olefin polymer, density of hydrogen changes between 1.03～5.38%v/v in the circulation gas.
Table 1
Yield strength, breaking tenacity and dart impact value use the physicals of the respective films product that olefin polymer prepares in the inventive method embodiment 1 and 2 obviously to be better than the physicals of Comparative Examples respective films product as can be seen from table 1.
In gel chromatograph (GPC) distribution plan that analysis obtains to polymer property, 10
6The weight-average molecular weight M of level
wHave tangible increase or conditions of streaking, the ultra-high molecular weight part that shows among the figure has improved the physicals of olefin polymer greatly.The M of phase emergencing copolymer among Fig. 3
n=2.3 * 10
4M
w=2.97 * 10
5M
z=1.86 * 10
6M
Z+1=4.04 * 10
6
From table 1 melt flow ratio MFR value as can be seen, the processing characteristics of olefin polymer obviously is better than the processing characteristics of phase emergencing copolymer in the Comparative Examples among the embodiment.
Claims (10)
1. a method of utilizing reactor to prepare polymkeric substance comprises that the polymerization temperature in the reactor is set to circulation change between high temperature dot and low warm spot, and there is one-period at least in described circulating in 6 hours, and described high temperature dot is higher more than 10 ℃ than low warm spot.
2. method according to claim 1, it is characterized in that: described high temperature dot is the temperature spot that is selected from 60～150 ℃, described low warm spot is the temperature spot that is selected from 20～80 ℃.
3. method according to claim 2, it is characterized in that: described high temperature dot is the temperature spot that is selected from 80～120 ℃, low warm spot is the temperature spot that is selected from 40～75 ℃; Preferred described high temperature dot is selected from 90～120 ℃, and the low temperature point is selected from 50～70 ℃; More preferably described high temperature dot is selected from 105～120 ℃, and the low temperature point is selected from 60～70 ℃.
4. according to any described method in the claim 1～3, it is characterized in that: there is one-period at least in described circulating in 5 hours, preferably had one-period in 4 hours at least.
5. according to any described method in the claim 1～3, it is characterized in that: polyreaction kept under the temperature value of each high temperature dot and/or low warm spot 0～4 hour, and preferred 0～2 hour, more preferably 0.5～1 hour.
6. according to any described method in the claim 1～3, it is characterized in that: the temperature changing speed between each high temperature dot and low warm spot is 0.1～8 ℃/min, preferred 1～6 ℃/min, more preferably 2～5 ℃/min.
7. according to any described method in the claim 1～3, it is characterized in that: use alkene homopolymerization or the described polymkeric substance of copolymerization, wherein alkene is selected from one or more in ethene, propylene, butylene, hexene, amylene, the octene.
8. according to any described method in the claim 1～3, it is characterized in that: preparation polymkeric substance employed reactor is a kind of in slurry-phase reactor, bulk reaction device, the gas-phase fluidized-bed reactor, preferred gas-phase fluidized-bed reactor.
9. according to any described method in the claim 1～3, it is characterized in that: the used catalyzer of preparation polymkeric substance is one or more in Ziegler-Natta catalyst, metallocene catalyst, Z-N and the metallocene composite catalyst, uses triethyl aluminum to be promotor during the preferred preparation polymkeric substance.
10. according to any described method in the claim 1～9, it is characterized in that: the melt flow ratio MFR of described polymkeric substance is flow index MI
21.6With melt index MI
2.16Ratio greater than 60.
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Citations (3)
| 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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Patent Citations (3)
| 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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