CN105542038A - Siloxane mixture, and method for regulating polymerization speed of small butch bulk polypropylene technology - Google Patents
Siloxane mixture, and method for regulating polymerization speed of small butch bulk polypropylene technology Download PDFInfo
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Abstract
The invention relates to the technical field of propylene polymerization in the petrochemical industry, and relates to a siloxane mixture, and a method for regulating the polymerization speed of a small butch bulk polypropylene technology. Raw materials of the siloxane mixture comprise a tetrasiloxy compound and trisiloxy compound, wherein the mass percentage of the tetrasiloxy compound in the siloxane mixture is 50-70%. The siloxane mixture is added in the preparation process of high fluidity polypropylene, so negative effects brought by massive introduction of hydrogen are avoided; and addition of the siloxane mixture delays concentrated release of the catalysis activity of a catalyst, prolongs the active time of the catalyst and reduces the peak polymerization rate of the catalyst without reducing the total catalysis efficiency of the catalyst or influencing the performances of prepared polypropylene, so process control of the small butch bulk polypropylene in the preparation of the high fluidity polypropylene is benefited.
Description
Technical field
The present invention relates to propylene polymerization technical field in petrochemical industry, is a kind of method of mixture of siloxanes and regulation and control small-entity polypropylene process polymerisation speed.
Background technology
Small-entity polypropylene technique, also known as interval hypoxic training technique, adopts single polymeric kettle periodical operation, for China researchs and develops voluntarily, is that refinery gas propylene resource is very abundant at home, but refinery distribution compare dispersion basis on grow up.Because this explained hereafter Technology is reliable, not very high to raw material propylene specification of quality, required catalyzer is domestic guaranteed, flow process is simple, reduced investment, produce effects fast, simple to operate, the three wastes are few, being applicable to the features such as China's actual conditions, obtaining develop rapidly in China, was also once that Economic development and the industry development of China serves indelible contribution over a period to come.But its shortcoming is single still batch operation, and relative to the multi-floating bodies continuous processing of current main flow, its production efficiency is low, technique variable range is narrow, and regulating measure is limited, and product grade is few, added value of product is low, can only produce the low-end product of low melting means in routine, faces huge competitive pressure.According to the feature of this unit scale I periodical operation, be more suitable for the few but product that added value is high of exploitation consumption.But existing a large amount of new technology, be all the continuous processing for multi-floating bodies, be difficult to realize on small scale bulk poly-unit.For small-entity polypropylene technique, owing to adopting single still periodical operation, again without ethylene copolymer, therefore product grade is few, and the adjustability of its product mainly concentrates on melting means and regulates, and therefore its product line trade mark is also just only embodied in the difference of melting means.And melting means is the sign of mobility in polymer processing, the mobility of polymkeric substance reflects its processibility whether had and range of application.Different working methods and range of application, different to the requirement of melting means, for injection moulding, melting means is higher, the mobility of polymkeric substance is better, is more conducive to processing, particularly some thin-wall products and large-caliber product, require so especially, in addition, good mobility, to reduction processing temperature, shorten shaping cycle all very favourable, obviously can reduce energy consumption and improve working (machining) efficiency, high workability polymeric articles has become a developing direction.As everyone knows, polypropylene (being called for short PP) is that propylene is polymerized and obtains under the effect of catalyst system, introduces hydrogen as chain-transfer agent, with Molecular regulator amount size, regulate and control the melting means size of PP thus in polymerization system.But, for the catalyst system of routine, due to the insensitivity that hydrogen is adjusted, improve the mobility of PP, need the intake rolling up hydrogen, because hydrogen is not only molecular weight regulator in polymerization system, and be a kind of activator, i.e. the increasing of hydrogen, not only molecular weight can be reduced, and the quick release of catalyst activity can be made, accelerate polymerization velocity, the quickening of polymerization velocity, particularly peak polymerization speed increases, mean that a large amount of of heat concentrate release, make troubles to the heat of removing of polymeric kettle, easily cause the out of control of polymerization temperature, there is temperature runaway and implode, bring potential safety hazard, therefore the operation easier of production process is greatly increased, therefore under existence conditions, utilize hydrogen to regulate the variable range of melting means limited.For small-entity polypropylene technique, realize high flow polypropylene, even the production of superelevation flow polypropylene, two approach can be had: (1) studies new catalyst system, improve hydrogen response, the polypropylene of high flowing can be prepared when a small amount of hydrogen; (2) in the situation that existing catalyst system is constant, when a large amount of hydrogen is introduced, how effectively to suppress hydrogen to the quick release of catalyst activity.Study the strong catalyst system of new hydrogen response and be not easy, being applied to suitability for industrialized production especially needs a very long process, and therefore approach (1) also needs to do a large amount of R&D works.And do not having under new catalyst system, by suitable Technology, avoid the quick release of catalyst activity, suppress peak polymerization speed, also can avoid temperature problem rambunctious, but existing document does not also have relevant report.The product melting means prepared by small-entity polypropylene technique is at present the highest at 30g/10min (230 DEG C, 2.16Kg) below, also cannot meet the polypropylene product of the production of high flow polypropylene, particularly more than 30g/10min.
Summary of the invention
The invention provides a kind of method of mixture of siloxanes and regulation and control small-entity polypropylene process polymerisation speed, overcome the deficiency of above-mentioned prior art, it is low that it effectively can solve the existing product melting means prepared by small-entity polypropylene technique, cannot meet the problem that high flow polypropylene is produced.
One of technical scheme of the present invention is realized by following measures: a kind of mixture of siloxanes, and raw material comprises four siloxy compounds and three siloxy compounds; Wherein: the mass percent of four siloxy compounds in mixture of siloxanes is 50% to 70%.
Here is the further optimization and/or improvements to one of foregoing invention technical scheme:
Above-mentioned mixture of siloxanes obtains as follows: by four siloxy compounds of aequum and three siloxy compound evenly after, obtain mixture of siloxanes.
Above-mentioned four siloxy compounds are tetrapropoxysilane or four butoxy silanes or tetramethoxy-silicane or tetraethoxysilane; Or/and three siloxy compounds are phenyl triethoxysilane or phenyltrimethoxysila,e.
Two of technical scheme of the present invention is realized by following measures: a kind of preparation method of mixture of siloxanes, carries out as follows: by four siloxy compounds of aequum and three siloxy compound evenly after, obtain mixture of siloxanes.
Here is the further optimization and/or improvements to foregoing invention technical scheme two:
Above-mentioned four siloxy compounds are tetrapropoxysilane or four butoxy silanes or tetramethoxy-silicane or tetraethoxysilane; Or/and three siloxy compounds are phenyl triethoxysilane or phenyltrimethoxysila,e.
Three of technical scheme of the present invention is realized by following measures: a kind of method using mixture of siloxanes to regulate and control small-entity polypropylene process polymerisation speed, carry out as follows: the propylene of aequum, catalyzer and mixture of siloxanes are added in polymerization reactor, then pass into hydrogen and carry out polyreaction, after polyreaction, obtain polypropylene through drying.
Here is the further optimization and/or improvements to foregoing invention technical scheme three:
The mass ratio of aforesaid propylene and catalyzer is 2500 to 3000:0.05, propylene and hydrogen mass ratio be 2500 to 3000:0.3 to 0.5, the add-on of mixture of siloxanes is 20% to 80% of electron donor in catalyzer; Or/and catalyzer is Ziegler-Natta catalyst; Or/and the temperature of polyreaction is 70 DEG C to 72 DEG C, and the pressure of polyreaction is 30bar to 32bar, polymerization reaction time is 2 little of 3 hours; Or/and drying temperature is 80 DEG C to 82 DEG C, time of drying is 23 little of 24 hours.
Above-mentioned in polymerization reactor, add propylene, catalyzer and mixture of siloxanes before, first discharge the oxygen in polymerization reactor and moisture.
Oxygen in above-mentioned discharge polymerization reactor and the method for moisture are carried out as follows: use nitrogen purging polymerization reactor, then the polymerization reactor after nitrogen purging is vacuumized, the time at every turn vacuumized is 5 minutes to 7 minutes, nitrogen purging and after vacuumizing and repeatedly carrying out 4 times to 5 times, with the hydrogen of 20bar to 21bar to polymerization reactor leakage detection, when polymerization reactor is air tight, to sequentially vacuumizing in polymerization reactor and purging by propylene gas.
First open the emptying valve of polymerization reactor after above-mentioned polyreaction, allow unreacted completely propylene gasify rapidly and discharge polymerization reactor, then use nitrogen purging polymerization reactor 3 times to 4 times, obtain polypropylene.
The present invention is by adding mixture of siloxanes when preparing high flow polypropylene, the negative impact that a large amount of introducings avoiding hydrogen bring; Simultaneously mixture of siloxanes add the concentrated release having delayed catalyst activity, extend the activity time of catalyzer, reduce catalyzer peak polymerization speed, but do not reduce total catalytic efficiency of catalyzer, not affecting prepared polyacrylic performance, being conducive to the technology controlling and process of small-entity polypropylene when preparing high flow polypropylene yet.
Accompanying drawing explanation
Accompanying drawing 1 is the polymerization kinetics curve of Z-N catalyzer in prior art propylene polymerization processes.
Accompanying drawing 2 is the polymerization kinetics curve of Z-N catalyzer when improving hydrogen intake in prior art propylene polymerization processes.
Accompanying drawing 3 is the Z-N polymerization kinetics curve adding mixture of siloxanes regulation and control in propylene polymerization processes of the present invention.
Embodiment
The present invention by the restriction of following embodiment, can not determine concrete embodiment according to technical scheme of the present invention and practical situation.
Embodiment 1, this mixture of siloxanes, raw material comprises four siloxy compounds and three siloxy compounds; Wherein: the mass percent of four siloxy compounds in mixture of siloxanes is 50% to 70%.
Embodiment 2, this mixture of siloxanes, raw material comprises four siloxy compounds and three siloxy compounds; Wherein: the mass percent of four siloxy compounds in mixture of siloxanes is 50% or 70%.
Embodiment 3, as the optimization of above-described embodiment, mixture of siloxanes obtains by following preparation method: by four siloxy compounds of aequum and three siloxy compound evenly after, obtain mixture of siloxanes.
Embodiment 4, as the optimization of above-described embodiment, four siloxy compounds are tetrapropoxysilane or four butoxy silanes or tetramethoxy-silicane or tetraethoxysilane; Or/and three siloxy compounds are phenyl triethoxysilane or phenyltrimethoxysila,e.Four siloxy compounds are preferably tetraethoxysilane; Three siloxy compounds are preferably phenyl triethoxysilane.
Embodiment 5, the method of this use mixture of siloxanes regulation and control small-entity polypropylene process polymerisation speed, carry out as follows: the propylene of aequum, catalyzer and mixture of siloxanes are added in polymerization reactor, then pass into hydrogen and carry out polyreaction, after polyreaction, obtain polypropylene through drying.
Embodiment 6, as the optimization of above-described embodiment, the mass ratio of propylene and catalyzer is 2500 to 3000:0.05, propylene and hydrogen mass ratio be 2500 to 3000:0.3 to 0.5, the add-on of mixture of siloxanes is 20% to 80% of electron donor in catalyzer; Or/and catalyzer is Ziegler-Natta catalyst; Or/and the temperature of polyreaction is 70 DEG C to 72 DEG C, and the pressure of polyreaction is 30bar to 32bar, polymerization reaction time is 2 little of 3 hours.
Embodiment 7, as the optimization of above-described embodiment, drying temperature is 80 DEG C to 82 DEG C, and time of drying is 23 little of 24 hours.
Embodiment 8, as the optimization of above-described embodiment, add propylene, catalyzer and mixture of siloxanes in polymerization reactor before, first discharges the oxygen in polymerization reactor and moisture.
Embodiment 9, as the optimization of above-described embodiment, oxygen in discharge polymerization reactor and the method for moisture are carried out as follows: use nitrogen purging polymerization reactor, then the polymerization reactor after nitrogen purging is vacuumized, the time at every turn vacuumized is 5 minutes to 7 minutes, nitrogen purging and after vacuumizing and repeatedly carrying out 4 times to 5 times, with the hydrogen of 20bar to 21bar to polymerization reactor leakage detection, when polymerization reactor is air tight, to sequentially vacuumizing in polymerization reactor and purging by propylene gas.
Embodiment 10, as the optimization of above-described embodiment, first opens the emptying valve of polymerization reactor after polyreaction, allow unreacted completely propylene gasify rapidly and discharge polymerization reactor, then use nitrogen purging polymerization reactor 3 times to 4 times, obtain polypropylene.
Prior art polypropylene (PP) is that propylene is polymerized and obtains under the effect of Ziegler-Natta catalyst system.The generalized concept of Z-N catalyzer is the bicomponent system of I-III race metal alkyl compound and IV-X group transition metal compound, and the most Z-N catalyzer for the preparation of PP contain the complex body of the titanium chloride of the various valence states of load on magnesium chloride.This TiCl
4/ MgCl
2complex body, adds organic internal electron donor (ID), is called catalyst precursor.In order to improve the taxis of polymkeric substance further, during polyreaction, in catalyst precursor and metal alkylide, adding a kind of auxiliary electron donor material, be called external electron donor (ED).Therefore, for Z-N catalyzer, conventional such formula is below expressed:
MgCl
2·ID·TiCl
4/AlEt
3·ED
In formula, ID refers to internal electron donor, and ED refers to external electron donor.
In the course of the polymerization process, usually also need to introduce hydrogen as chain-transfer agent, with Molecular regulator amount size, regulate and control the melting means size of PP thus.Hydrogen, except regulating polypropylene molecule amount size, can also affect the catalytic activity of catalyzer.
For the catalyzer of industrial application, except its catalytic activity understood by needs, also must understand its catalytic kinetics.By dynamic (dynamical) research, grasp the speed of reaction, the suction/to one's heart's content condition of heat, the conversion situation of raw material, the problems such as a reaction effective reaction times.
About the research of the polymerization kinetics of Z-N catalyst propylene, existing a large amount of documents exists, and Fig. 1 shows the dynamic process when its typical polymerization, and Fig. 1 is the polymerization kinetics curve of Z-N catalyzer in prior art propylene polymerization processes.Can find from Fig. 1, rate of polymerization increases gradually in the early stage, and reach a peak value, thereafter activity reduces gradually, rate of polymerization also reduces gradually, decay of activity is not until have activity, and the polypropylene melting means using this catalyzer and polymerization technique prepared on small-entity polypropylene device is about 7g/10min, belongs to conventional melting means product.
If the intake of hydrogen is increased by 1 times, so its polymerization kinetics is for shown in Fig. 2, and accompanying drawing 2 is the polymerization kinetics curve of Z-N catalyzer when improving hydrogen intake in prior art propylene polymerization processes.As can see from Figure 2, obviously, along with the increase of hydrogen intake, polymerization kinetics curve shape does not change, but peak polymerization speed improves nearly 3 times, can see simultaneously yet, polymerization velocity decay is also very rapid, substantially decays to very low speed at 2.5hr.Therefore, strengthen the add-on of hydrogen, the catalytic activity accelerating catalyzer concentrates release, and this also means that heat of polymerization also can discharge in the short period of time fast, causes the quick rising of polymerization temperature.By the intake of hydrogen is improved 1 times, polypropylene product melting means prepared by small scale bulk poly-unit is at 12g/10min, and melting means is not high.
We are polymerized top temperature that temperature in the kettle is raised in 3min to weigh heat release speed under can being used in identical cooling conditions, table 1 is the polymerization result in prior art propylene polymerization processes under different hydrogen intake, as can be seen from Table 1, the raising of hydrogen makes polymerization temperature in the kettle rise fast, if polymeric kettle remove hot scarce capacity time, just there will be temperature runaway, cause security incident, therefore, the intake by improving hydrogen in small-entity polypropylene device is prepared high melting means polypropylene and is difficult to realize.
In the method for regulation and control polymerization velocity, known method in polymerization system, adds quencher make catalyst deactivation, and this method is phase after polymerisation, such as in system, passes into CO, make catalyst deactivation and stop, obvious this method to be applied to the situation preparing high flow polypropylene.
In order to prepare high flow polypropylene on small-entity polypropylene device, investigator of the present invention conducts in-depth research, its basic point of departure is: keep existing Z-N catalyst system, when a large amount of hydrogen adds, the method of exploitation controllable rate of polymerization, slow down the concentrated release of catalyst activity, allow the release of catalyst activity with a kind of evenly mode, so just can control the temperature in polymeric kettle, and prepare high flow polypropylene, do not reduce the catalytic efficiency of catalyzer simultaneously, do not affect polyacrylic stuctures and properties yet.
The present invention experimental studies have found that through a large amount of, and when adding the mixture of siloxanes containing three and four silica groups to polymerization system in system, polymerization velocity there occurs obvious beyond thought effect.Introduce the polymerization kinetics curve after this mixture of siloxanes as shown in Figure 3, Fig. 3 is the Z-N polymerization kinetics curve adding mixture of siloxanes regulation and control in propylene polymerization processes of the present invention.As can be seen from Figure 3, the present invention can prepare the polypropylene product of melting means more than 50g/10min, polymerization result in propylene polymerization processes of the present invention under the lower high hydrogen intake of mixture of siloxanes regulation and control is as shown in table 2, as can be seen from Table 2, peak polymerization speed in polymerization process reduces greatly, and the hold-time of activity is extended.
Therefore, the present invention in the situation of higher hydrogen gas intake, can slow down the concentrated release of catalyst activity, avoids polymerization temperature situation rambunctious.And the organosilicon mixture added does not affect the overall catalytic activity of catalyzer, does not affect the performance of polypropylene product yet.
Polymerization experiment
Component A: catalyst precursor is commercially available N catalyst series for the catalyst system in present specification, and this catalyzer is widely used in, on domestic each polypropylene plant, belonging to forth generation high activated catalyst, with MgCl
2carrier loaded upper TiCl
4catalyzer, in catalyzer, a point rate of Ti is about 2.2wt%, unless stated otherwise, below the amount about 50mg of component A in the embodiment of the present invention;
B component: promotor, triethyl aluminum, is made into the hexane solution that concentration is 0.88mol/L during use;
Component C: external electron donor, DDS;
Component D: mixture of siloxanes, not specified, be 60% (quality) that four siloxy compounds account for mixture of siloxanes ratio;
Propylene: the propylene for testing is polymerization-grade, purity is 99.5%, and major impurity is propane;
Hydrogen: purity is 99.999%, hydrogen in reaction addition is as the criterion with hydrogen partial pressure 2bar under normal temperature;
High Purity Nitrogen: purity 99.999%.
When this mixture of siloxanes is applied to polymerization system, its usage quantity follows following principle: M (mixture of siloxanes)/(M (mixture of siloxanes)+M (external electron donor))=10% to 90%.
Embodiment 11
Test by aforementioned polymeric, selected component D is the mixture that phenyl triethoxysilane (PTES) and tetraethoxysilane (TEOS) form, wherein TEOS accounting 60%, its add-on is: (M (PTES)+M (TEOS))/((M (PTES)+M (TEOS))+M (DDS))=50%, polymerization result is in table 3.
Embodiment 12
The implementation process identical with enforcement 11, except TEOS accounting 80%, polymerization result is in table 3.
Embodiment 13
The implementation process identical with enforcement 11, add-on is: (M (PTES)+M (TEOS))/((M (PTES)+M (TEOS))+M (DDS))=30%, polymerization result is in table 3.
Embodiment 14
The implementation process identical with enforcement 11, add-on is: (M (PTES)+M (TEOS))/((M (PTES)+M (TEOS))+M (DDS))=70%, polymerization result is in table 3.
Embodiment 15
The implementation process identical with enforcement 11, except the intake of hydrogen is 4bar, polymerization result is in table 3.
Comparative example 1
The implementation process identical with enforcement 11, except not adding the D component containing many silica group, polymerization result is in table 3.
Comparative example 2
The implementation process identical with enforcement 11, except only using PTES, and M (PTES)/(M (PTES)+M (DDS))=50%, polymerization result is in table 3.
Comparative example 3
The implementation process identical with enforcement 11, except only using TEOS, and M (TEOS)/(M (TEOS)+M (DDS))=50%, polymerization result is in table 3.
Comparative example 4
The implementation process identical with enforcement 11, add-on is: (M (PTES)+M (TEOS))/((M (PTES)+M (TEOS))+M (DDS))=5%, polymerization result is in table 3.
Comparative example 5
The implementation process identical with enforcement 11, add-on is: (M (PTES)+M (TEOS))/((M (PTES)+M (TEOS))+M (DDS))=95%, polymerization result is in table 3.
Can be seen by table 3, when in mixture of siloxanes, TEOS accounting is higher, ability of regulation and control is stronger, but prepared polypropylene degree of isotacticity can reduce, and catalyst activity also has decline to a certain degree; PTES then ability of regulation and control is more weak, the active decline also had to a certain degree, but can keep certain degree of isotacticity.Add mixture of siloxanes, not only have stronger ability of regulation and control, prepared polypropylene degree of isotacticity is higher, also can keep the activity of catalyzer, may be used for the production of high flow polypropylene.
In sum, by adding mixture of siloxanes when preparing high flow polypropylene, the negative impact that a large amount of introducings avoiding hydrogen bring; Simultaneously mixture of siloxanes add the concentrated release having delayed catalyst activity, extend the activity time of catalyzer, reduce catalyzer peak polymerization speed, but do not reduce total catalytic efficiency of catalyzer, not affecting prepared polyacrylic performance, being conducive to the technology controlling and process of small-entity polypropylene when preparing high flow polypropylene yet.
Above technical characteristic constitutes embodiments of the invention, and it has stronger adaptability and implementation result, can increase and decrease non-essential technical characteristic according to actual needs, meet the demand of different situations.
Table 1
| Hydrogen partial pressure 1bar | Hydrogen partial pressure 2bar | |
| 3min polymeric kettle top temperature (DEG C) | 73 | 80 |
| Polypropylene melting means (g/10min) | 7 | 12 |
Table 2
| Hydrogen partial pressure 5bar | Hydrogen partial pressure 8bar | |
| 3min polymeric kettle top temperature (DEG C) | 71 | 73 |
| Polypropylene melting means (g/10min) | 62 | 86 |
Table 3
Claims (9)
1. a mixture of siloxanes, is characterized in that raw material comprises four siloxy compounds and three siloxy compounds; Wherein: the mass percent of four siloxy compounds in mixture of siloxanes is 50% to 70%.
2. mixture of siloxanes according to claim 1, is characterized in that obtaining as follows: by four siloxy compounds of aequum and three siloxy compound evenly after, obtain mixture of siloxanes.
3. mixture of siloxanes according to claim 1 and 2, is characterized in that four siloxy compounds are tetrapropoxysilane or four butoxy silanes or tetramethoxy-silicane or tetraethoxysilane; Or/and three siloxy compounds are phenyl triethoxysilane or phenyltrimethoxysila,e.
4. a preparation method for mixture of siloxanes according to claim 3, is characterized in that carrying out as follows: by four siloxy compounds of aequum and three siloxy compound evenly after, obtain mixture of siloxanes.
5. one kind uses the method for the mixture of siloxanes regulation and control small-entity polypropylene process polymerisation speed according to claim 1 or 2 or 3, it is characterized in that carrying out as follows: the propylene of aequum, catalyzer and mixture of siloxanes are added in polymerization reactor, then pass into hydrogen and carry out polyreaction, after polyreaction, obtain polypropylene through drying.
6. the method for regulation and control small-entity polypropylene process polymerisation speed according to claim 5, it is characterized in that the mass ratio of propylene and catalyzer is 2500 to 3000:0.05, propylene and hydrogen mass ratio be 2500 to 3000:0.3 to 0.5, the add-on of mixture of siloxanes is 20% to 80% of electron donor in catalyzer; Or/and catalyzer is Ziegler-Natta catalyst; Or/and the temperature of polyreaction is 70 DEG C to 72 DEG C, and the pressure of polyreaction is 30bar to 32bar, polymerization reaction time is 2 little of 3 hours; Or/and drying temperature is 80 DEG C to 82 DEG C, time of drying is 23 little of 24 hours.
7. the method for the regulation and control small-entity polypropylene process polymerisation speed according to claim 5 or 6, before it is characterized in that adding propylene, catalyzer and mixture of siloxanes in polymerization reactor, first discharges the oxygen in polymerization reactor and moisture.
8. the method for regulation and control small-entity polypropylene process polymerisation speed according to claim 7, the method that it is characterized in that discharging oxygen in polymerization reactor and moisture is carried out as follows: use nitrogen purging polymerization reactor, then the polymerization reactor after nitrogen purging is vacuumized, the time at every turn vacuumized is 5 minutes to 7 minutes, nitrogen purging and after vacuumizing and repeatedly carrying out 4 times to 5 times, with the hydrogen of 20bar to 21bar to polymerization reactor leakage detection, when polymerization reactor is air tight, to sequentially vacuumizing in polymerization reactor and purging by propylene gas.
9. the method for the regulation and control small-entity polypropylene process polymerisation speed according to claim 5 or 6 or 7 or 8, the emptying valve of polymerization reactor is first opened after it is characterized in that polyreaction, allow unreacted completely propylene gasify rapidly and discharge polymerization reactor, then use nitrogen purging polymerization reactor 3 times to 4 times, obtain polypropylene.
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| WO1997043321A1 (en) * | 1996-05-15 | 1997-11-20 | Borealis A/S | Stereospecific catalyst system for olefin polymerization and multistaged polymerization processes using this catalyst system |
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