CN1560093A - Preparation process of polypropylene with wide molecule weight distribution - Google Patents
Preparation process of polypropylene with wide molecule weight distribution Download PDFInfo
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- CN1560093A CN1560093A CNA2004100141947A CN200410014194A CN1560093A CN 1560093 A CN1560093 A CN 1560093A CN A2004100141947 A CNA2004100141947 A CN A2004100141947A CN 200410014194 A CN200410014194 A CN 200410014194A CN 1560093 A CN1560093 A CN 1560093A
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Abstract
The invention is a method of preparing polypropylene with a broad distribution of molecular weight, improving the HYPOL polypropylene producing process in three-well oiling development, adding a flash evaporation jar in liquid-phase polymerizing kettle D-202 and gas-phase polymerizing kettle, adopting improved producing devices and multi-kettle segment polymerizing method, where the first segment liquid-phase monomer polymerization is made at 40-70 deg.C to generate polypropylene with high or ultrahigh molecular weight and the second segment liquid-phase monomer polymerization is made at 70-90 deg.C and in bulk percent of hydrogen gas 0.5-30%, to generate low-molecular weight polypropylene. This polypropylene contains a certain quantity of high-molecular weight polypropylene, and has relatively high rigidity and melt strength, better fluidity and thermal deforming temperature and better molding processing property, able to be used on the occasions in need of higher rigidity of polypropylene.
Description
Technical field
The present invention relates to the preparation of polyolefins method, specifically, relate to the polyacrylic preparation method of wide molecular weight distribution.
Background technology
High molecular in the polymkeric substance of wide molecular weight distribution partly makes polymkeric substance have higher melt strength, and lower molecular weight partly makes polymkeric substance have better machining property and melt flow property, so the excellent combination property of mechanical property and processability, broad molecular weight distribution polypropylene is one of the latest developments in recent polypropylene technology field.Though bimodal polyethylene resins just developed since the mid-90, obtained remarkable progress so far and obtained and used more widely, the research and development of broad molecular weight distribution polypropylene are just shown up prominently.Mainly contain European Borealis, Hoechst, Basell company, unit such as Japanese grand chemical fibre Co., Ltd., Mitsui KCC is in development research.
Prepare at present the method that broad molecular weight distribution polypropylene mainly adopts stage feeding polymerization, at high (or superelevation) molecular weight polypropylene of fs preparation earlier, the polypropylene for preparing lower molecular weight in subordinate phase, thereby make the molecular weight distribution broad of final polymkeric substance, rigidity, heat-drawn wire, melt strength etc. are higher.Comprise 10-50% (quality) higher molecular weight polypropylene, 10-89% (quality) lower molecular weight polypropylene and 1-40% (quality) ethylene/alpha-olefin copolymer as the disclosed polypropylene block copolymer resin of application number: CN00104699.3, has higher melt tension force, moldability is better, and rigidity and shock resistance high comprehensive performance, can be molded at a high speed have the shape stability height, large size moulded product that appearance property is good.
The bimodal polypropylene technology of the Borstar of Northern Europe Borealis company exploitation adopts unique annular-pipe reactor and the placed in-line technical process production of Gas-phase reactor high-performance, bimodal polypropylene product cheaply, some Patent publish that Borealis company is recent obtain the method for wide molecular weight distribution, bimodal acrylic resin.At US6, adopt the multi-stage polymeric prepared in 300,420, preparation Mw is 2 in first reactor, 000,000-4,000,000 higher molecular weight multipolymer, preparation lower molecular weight multipolymer in remaining reactor, final copolymer composition molecular weight distribution MWD is 6-15.At document WO 200,100,416,6A1 18 Jan 2001,24pp. in, disclose employing Ziegler-Natta type catalyzer, in the reactive system of the composition of mutual placed in-line bulk reaction device (more than or equal to 1) and Gas-phase reactor (more than or equal to 1), prepared the method for broad molecular weight distribution polypropylene.
In the technology of these productions, have and use the propylene copolymer of 2 reactors in series (can use different combination of reactors such as gas phase-gas phase, slurries-slurries, body-gas phase, body-body) preparation to have the comonomer distribution of high molecular, wide molecular weight distribution and improvement, the higher molecular weight multipolymer Mw of preparation reaches 2 in the fs, 000,000-4,000,000, final copolymer composition molecular weight distribution MWD is 6-15, and the ratio of higher molecular weight multipolymer and lower molecular weight multipolymer is 40/60-70/30.Can be used to produce moulded parts such as tubing, pipe fitting, hollow piece, sheet material etc., the tubing of producing with conventional processing units not only smooth surface, processing performance is good, and intensity height, hardness and creep resistance excellent combination property.
Bimodal polypropylene contains a certain amount of high (or superelevation) molecular weight segment, has improved rigidity, thermotolerance, creep-resistant property and the melt strength of material.With add nucleator with blend method and compare, its performance increase rate is big, can be mass-produced, cost is lower, add the nucleator blend as this contain in a certain amount of high (or superelevation) molecular weight polypropylene, its modulus in flexure improves nearly one times, and thermal distortion is increased to 148 ℃.
Summary of the invention
The objective of the invention is to utilize the equipment of HYPOL production technique that a kind of manufacture method of broad molecular weight distribution polypropylene is provided.
The present invention has utilized existing HYPOL production process equipment.The HYPOL production technique is the polypropylene production technique of Mitsui oiling exploitation, its equipment, schematic flow sheet are as shown in Figure 1, for the ease of producing the polypropylene that contains height (or superelevation) molecular weight in the continuous method of Zai Even, existing HYPOL production process equipment can not satisfy the production needs, need do some improvement to production unit.One of the object of the invention implementation is as follows:
A kind of manufacture method of broad molecular weight distribution polypropylene, it adopts the stage feeding polymerization method: first section, liquid-phase bulk polymerization, 40～70 ℃ of temperature of reaction, 0.5～90 minute residence time, do not add hydrogen, second section, vapour phase polymerization, 70～90 ℃ of temperature of reaction, 60～120 minutes residence time, H2 concentration is at 0.5～30% (V/V), the technical process of present method can be as shown in Figure 2, promptly adopt two liquid phase polymerizers and two vapor phase polymerizers, the material that comes out from the second liquid phase polymerizer D-202 enters a flash tank Q-1, and the material after the flash distillation enters the 3rd vapor phase polymerizer D-203 reaction, and unnecessary propylene enters first liquid phase polymerizer D-201 reaction through propylene pump P-C3 after the flash distillation.A large amount of liquid propylenes of transforming the preceding second liquid phase polymerizer D-202 directly enter the 3rd vapor phase polymerizer D-203, and the hydrogen in unnecessary then propylene and the still enters the first liquid phase polymerizer D-201 from the 3rd vapor phase polymerizer D-203; A large amount of liquid propylenes of transforming the back second liquid phase polymerizer D-202 enter the Q-1 flash tank, unnecessary propylene enters the first liquid phase polymerizer D-201 through pump P-C3, avoided the hydrogen in the 3rd vapor phase polymerizer D-203 to sneak into the first liquid phase polymerizer D-201 and the second liquid phase polymerizer D-202 like this, thereby can utilize appropriate catalyst and catalyst proportion to generate a certain amount of high molecular weight polypropylene at D-201 still and D-202 still.
The implementation of the object of the invention two as follows:
A kind of manufacture method of broad molecular weight distribution polypropylene adopts the stage feeding polymerization method: first section, liquid-phase bulk polymerization, 40～70 ℃ of temperature of reaction, 0.5～90 minute residence time, hydrogen does not add, second section, vapour phase polymerization, 70～90 ℃ of temperature of reaction, 60～120 minutes residence time, H
2Concentration is at 0.5～30% (V/V), the technical process of present method can be as shown in Figure 3, promptly also adopt two liquid phase polymerizers and two vapor phase polymerizers, the material that comes out from the first liquid phase polymerizer D-201 enters a flash tank Q-1, material after the flash distillation enters second liquid phase polymerizer D-202 reaction, and unnecessary propylene enters first liquid phase polymerizer D-201 reaction through propylene pump P-C3 after the flash distillation.Unnecessary propylene with the 3rd vapor phase polymerizer D-203 enters the second liquid phase polymerizer D-202 simultaneously, the different efficacies of one of present method and method is to have only the first liquid phase polymerizer D-201 to generate high molecular weight polypropylene, and one of high molecular weight polypropylene proportion ratio method is few in the generation broad molecular weight distribution polypropylene.
Therefore, technical scheme of the present invention is as follows.
A kind of batch production method of broad molecular weight distribution polypropylene, it is made up of the following step:
A. liquid-phase bulk polymerization: in polymermaking autoclave, add liquid propylene and catalyzer, carry out polymerization at 40～70 ℃, polymerization time 30～90 minutes,
B. vapour phase polymerization: in above-mentioned reaction mixture, feed hydrogen, the volume by volume concentration of hydrogen was 0.5～30%, 70～90 ℃ of polymerizations 60～120 minutes.
A kind of continuous production method of broad molecular weight distribution polypropylene, it is made up of the following step:
A. liquid-phase bulk polymerization: in liquid phase polymerizer, add liquid propylene, catalyzer, carry out polymerization at 40～70 ℃, mean residence time is 30～90 minutes in still,
B. flash distillation: A step polymeric material enters a flash tank flash distillation, and temperature 30-70 ℃, pressure 4.5-0.1MPa, the propylene that flashes off is sent liquid phase polymerizer back to by the propylene recycle pump,
C. fluidized bed gas-phase polymerization: the material after flash distillation carries out vapour phase polymerization, feeds hydrogen, 70～90 ℃ of polymerization temperatures, polymerization 60～120 minutes, H
2Concentration is 0.5～30% (V/V).
The continuous production method of above-mentioned broad molecular weight distribution polypropylene, in steps A, two liquid phase polymerizers can be arranged, the first liquid phase polymerizer polymerization temperature is controlled at 50～70 ℃, the residence time was controlled at 15～45 minutes, the second reactor polymerization temperature is controlled at 50～70 ℃, and the residence time was controlled at 15～45 minutes, carries out step B flash distillation then.
The continuous production method of above-mentioned broad molecular weight distribution polypropylene, in step C, two fluidized bed gas-phase polymerization stills can be arranged, the 3rd vapor phase polymerizer pressure-controlling is at 1.0～2.5MPa, and polymerization temperature is controlled at 60～90 ℃, and the residence time was controlled at 15～60 minutes, the hydrogen volume specific concentration is 2～10%, the 4th vapor phase polymerizer pressure-controlling is at 0.8～2.0MPa, and polymerization temperature is controlled at 60～90 ℃, and the hydrogen volume specific concentration is 2～40%.
The characteristics of present method be propylene in first, second polymeric kettle polymerization after flash distillation, enter the 3rd vapor phase polymerizer again, trimerization still like this directly is not communicated with first, second polymeric kettle, the hydrogen of trimerization still can not enter first, second polymeric kettle, has guaranteed that the propylene of first, second polymeric kettle can aggregate into the polypropylene of high molecular or ultra-high molecular weight.
The continuous production method of above-mentioned broad molecular weight distribution polypropylene, step B flash distillation also can be placed on after first polymeric kettle, so, propylene enters the flash tank flash distillation after the first polymeric kettle polymerization, the propylene that flashes off returns the reaction of first polymeric kettle by the propylene recycle pump, material after the flash distillation enters second polymeric kettle, at 60～75 ℃, the residence time is controlled at carried out liquid-phase bulk polymerization in 15～45 minutes, enter the trimerization still then and carry out vapour phase polymerization, the unnecessary propylene of trimerization still is sent the reaction of second polymeric kettle back to by the propylene recycle pump.
Above-mentioned method has guaranteed that the propylene of first polymeric kettle can aggregate into the polypropylene of high molecular or ultra-high molecular weight.
With polymeric method stage by stage, high (superelevation) molecular weight polypropylene of elder generation's polymerization preparation, feed molecular weight regulator hydrogen then, low-molecular-weight polypropylene during polymerization generates, can make and contain height (surpassing) high-molecular weight polypropylene, its molecular weight distribution broad, molecular weight distribution mw/mn are 8～20, and this polyacrylic rigidity, heat-drawn wire and melt strength are better than common polypropylene.Polymkeric substance has higher melt strength, and lower molecular weight partly makes polymkeric substance have better machining property and melt flow property, such block copolymerization polypropylene has rigidity and heat-drawn wire preferably, and high impulse strength, the fine balance of the rigidity of material and toughness, the excellent property that this polypropylene is comprehensive.
Description of drawings
Fig. 1 is existing HYPOL technological process of production figure, and wherein: D-201 is first polymeric kettle, and D-202 is second polymeric kettle, and D-203 is the trimerization still, and D-204 is the 4th polymeric kettle, and P-C3 is the propylene recycle pump;
Fig. 2 is the technological process of production figure of production broad molecular weight distribution polypropylene of the present invention, and wherein: D-201 is first polymeric kettle, and D-202 is second polymeric kettle, D-203 is the trimerization still, D-204 is the 4th polymeric kettle, and P-C3 is the propylene recycle pump, and Q-1 is a flash tank;
Fig. 3 is the technological process of production figure of production broad molecular weight distribution polypropylene of the present invention, and wherein: D-201 is first polymeric kettle, and D-202 is second polymeric kettle, D-203 is the trimerization still, and D-204 is the 4th polymeric kettle, and P-C3 is the propylene recycle pump, P-C31 is the propylene recycle pump, and Q-1 is a flash tank.
Fig. 4 is the graph of molecular weight distribution of simultaneous test 1 products obtained therefrom;
Fig. 5 is the graph of molecular weight distribution of embodiment 1 products obtained therefrom;
Fig. 6 is the graph of molecular weight distribution of embodiment 3 products obtained therefroms.
Embodiment
Single still aggregation test carries out in the 10L polymermaking autoclave among the embodiment, carries out in the HYPOL processing unit of pilot plant test after improvement.
Aggregation test carries out on 10L polymermaking autoclave testing apparatus, polymeric kettle with nitrogen purging after, extract gas in the polymeric kettle out with vacuum pump.Catalyzer, triethyl aluminum, dicyclopentyl dimethoxyl silane etc. join in the tubular catalyst feeder under nitrogen protection; liquid propene enters polymeric kettle after the surge pump pressurization; propylene measures with electronic balance; hydrogen is with the metering of hydrogen pressure pan pressure difference, and temperature of reaction and mixing speed are controlled by the DCS system.After material adds, be rapidly heated, liquid-phase bulk polymerization is carried out in outlet temperature control at a certain temperature, stirring velocity is 200 rev/mins, behind the polymerization certain hour, the gas composition in the polymeric kettle is emitted material by online gas chromatographic detection by baiting valve, dry, weigh, add the auxiliary agent granulation, analyze.
Pilot plant test adopts Fig. 2, technical process shown in Figure 3, fresh propylene, catalyzer, triethyl aluminum, dicyclopentyl dimethoxyl silane etc. are added the D-201 still respectively through volume pump, carry out liquid-phase bulk polymerization at D-201 still and D-202 still, carry out vapour phase polymerization at D-203 still and D-204 still, and adding a large amount of hydrogen, the gas composition in the polymeric kettle is by online gas chromatographic detection and control.
Test event has:
Mechanical property adopts the GB1039-92 standard testing,
Tensile strength adopts the GB/T1040-92 standard testing.
Modulus in flexure adopts the GB9341-88 standard testing.
Cantilever beam impact strength adopts GB1843-80 (89) standard testing.
Heat-drawn wire adopts GB1634-79 (89) standard testing.
Rockwell hardness adopts the GB9342-88 standard testing.
Ziegler-Natta type catalyst n, this catalyzer are commercial polypropylene catalyst, and manufacturers is the China Petrochemical Industry Beijing Chemical Research Institute, and Ti content is in 2.0% (weight).Promotor: triethyl aluminum AT, prepare its safe concentration 0.88mol/L with hexane before using; Electron donor: dicyclopentyl dimethoxyl silane is diluted to the hexane solution of 110mmol/L with it before using.
Accurate weighing N type catalyzer 60.0mg, triethyl aluminium solution 3.0ml, dicyclopentyl dimethoxyl silane solution 2.0ml join under nitrogen protection in the catalyzer feeder.Add propylene 3000g., be rapidly heated, temperature is controlled at 60 ± 1 ℃ and carries out mass polymerization, stirring velocity is 200 rev/mins, behind the polyase 13 0 minute, get the homopolymer polymer sample a little, carry out the limiting viscosity analysis of polymkeric substance after the drying, see Table 1, feed hydrogen 45L then, polymerization temperature is controlled at 75 ℃, and the gas composition in the polymeric kettle is by online gas chromatographic detection, and polymerization was emitted material by baiting valve after 120 minutes, dry, weigh, polymkeric substance 2498g, add the auxiliary agent granulation, analyze, the results are shown in Table 1, molecular weight distribution sees Table 2 and Fig. 5.
Embodiment 2, accurate weighing N catalyzer 60.0mg, and triethyl aluminium solution 3.0ml, dicyclopentyl dimethoxyl silane solution 2.0ml join in the catalyzer feeder under nitrogen protection.Add propylene 3000g., be rapidly heated, temperature is controlled at 60 ± 1 ℃ and carries out mass polymerization, stirring velocity is 200 rev/mins, after the polymerization 45 minutes, get the homopolymer polymer sample a little, carry out the limiting viscosity analysis of polymkeric substance after the drying, see Table 1, feed hydrogen 45L then, polymerization temperature is controlled at 75 ℃, and the gas composition in the polymeric kettle is by online gas chromatographic detection, polymerization was emitted material by baiting valve in 120 minutes, dry, weigh, polymkeric substance 2480g, add the auxiliary agent granulation, analyze, the results are shown in Table 1, molecular weight distribution sees Table 2.
The accurate weighing N of embodiment 2-1. type catalyzer 60.0mg, triethyl aluminium solution 3.0ml, dicyclopentyl dimethoxyl silane solution 2.0ml join in the catalyzer feeder under nitrogen protection.Add propylene 3000g., be rapidly heated, temperature is controlled at 65 ± 1 ℃ and carries out mass polymerization, stirring velocity is 200 rev/mins, after the polymerization 45 minutes, get the homopolymer polymer sample a little, carry out the limiting viscosity analysis of polymkeric substance after the drying, the results are shown in Table 1, feed hydrogen 45L then, polymerization temperature is controlled at 75 ℃, gas composition in the polymeric kettle is by online gas chromatographic detection, and polymerization was emitted material by baiting valve in 120 minutes, dry, weigh, polymkeric substance 2458g, the granulation of adding auxiliary agent, analyze, the results are shown in Table 1, table 2.
The accurate weighing N of embodiment 2-2. type catalyzer 60.0mg, triethyl aluminium solution 3.0ml, dicyclopentyl dimethoxyl silane solution 2.0ml join in the catalyzer feeder under nitrogen protection.Add propylene 3000g., be rapidly heated, temperature is controlled at 55 ± 1 ℃ and carries out mass polymerization, stirring velocity is 200 rev/mins, after the polymerization 45 minutes, get the homopolymer polymer sample a little, carry out the limiting viscosity analysis of polymkeric substance after the drying, the results are shown in Table 1, feed hydrogen 45L then, polymerization temperature is controlled at 75 ℃, gas composition in the polymeric kettle is by online gas chromatographic detection, and polymerization was emitted material by baiting valve in 120 minutes, dry, weigh, polymkeric substance 2433g, the granulation of adding auxiliary agent, analyze, the results are shown in Table 1, table 2.
The accurate weighing N of embodiment 2-3. type catalyzer 60.0mg, triethyl aluminium solution 3.0ml, dicyclopentyl dimethoxyl silane solution 2.0ml join in the catalyzer feeder under nitrogen protection.Add propylene 3000g., be rapidly heated, temperature is controlled at 50 ± 1 ℃ and carries out mass polymerization, stirring velocity is 200 rev/mins, after the polymerization 45 minutes, get the homopolymer polymer sample a little, carry out the limiting viscosity analysis of polymkeric substance after the drying, the results are shown in Table 1, feed hydrogen 45L then, polymerization temperature is controlled at 75 ℃, gas composition in the polymeric kettle is by online gas chromatographic detection, and polymerization was emitted material by baiting valve in 120 minutes, dry, weigh, polymkeric substance 2233g, the granulation of adding auxiliary agent, analyze, the results are shown in Table 1, table 2.
Embodiment 3, accurate weighing N catalyzer 60.0mg, and triethyl aluminium solution 3.0ml, dicyclopentyl dimethoxyl silane solution 2.0ml join in the catalyzer feeder under nitrogen protection.Add propylene 3000g., be rapidly heated, temperature is controlled at 60 ± 1 ℃ and carries out mass polymerization, stirring velocity is 200 rev/mins, after the polymerization 60 minutes, get the homopolymer polymer sample a little, carry out the limiting viscosity analysis of polymkeric substance after the drying, see Table 1, feed hydrogen 60L then, polymerization temperature is controlled at 75 ℃, and the gas composition in the polymeric kettle is by online gas chromatographic detection, and polymerization was emitted material by baiting valve in 120 minutes, dry, weigh, polymkeric substance 2580g, add the auxiliary agent granulation, analyze, the results are shown in Table 1 and Fig. 6.
Embodiment 4.N catalyzer was with 1.0g/ hour, triethyl aluminum and dicyclopentyl dimethoxyl silane are that the ratio of 150mol/10mol/1mol adds the first polymeric kettle D-201 respectively with volume pump in the Al/Si/Ti ratio, adding propylene (per hour add-on is at 30kg) polymerization temperature simultaneously is controlled at 65 ± 1 ℃ and carries out mass polymerization, stirring velocity is 200 rev/mins, mean residence time is 15 minutes, take out small amount of polymer from thief hole and carry out analytical test, the results are shown in Table 2, the material that comes out from the first polymeric kettle D-201 enters flash tank Q-1, material enters the second polymeric kettle D-202 after the flash distillation, the propylene that flashes off enters the first polymeric kettle D-201 through propylene recycle pump P-C3, the second polymeric kettle D-202 polymerization temperature is controlled at 58 ± 1 ℃, mean residence time was controlled at 30 minutes, take out a small amount of poly-analytical test that carries out from thief hole, the results are shown in Table 2, material enters the 3rd vapor phase polymerizer D-203 then, feed a large amount of hydrogen, and control hydrogen is at 12% (v/v) in the gas composition, polymerization temperature is controlled at 80 ℃, pressure-controlling is at 2.0～1.6Mpa, gas composition in the polymeric kettle is by online gas chromatographic detection, mean residence time was controlled at 30 minutes, polymer material enters the 4th polymeric kettle D-204 again and carries out vapour phase polymerization, control hydrogen is at 10% (v/v) in the gas composition, polymerization temperature is controlled at 75 ℃, pressure-controlling is at 1.6～1.4Mpa, gas composition in the polymeric kettle is by online gas chromatographic detection, mean residence time was controlled at 30 minutes, emit material, polymer output is 20kg/ hour, drying, add the auxiliary agent granulation, analyze, the results are shown in Table 1, molecular weight distribution sees Table 2.
Simultaneous test 2.N catalyzer was with 1.0g/ hour, triethyl aluminum and dicyclopentyl dimethoxyl silane are that the ratio of 150mol/10mol/1mol adds the first polymeric kettle D-201 respectively with volume pump in the Al/Si/Ti ratio, add propylene (per hour add-on 30kg) simultaneously, polymerization temperature is controlled at 68 ± 1 ℃ and carries out mass polymerization, density of hydrogen is controlled at 2%, stirring velocity is 200 rev/mins, mean residence time is 15 minutes, enter the second polymeric kettle D-202, polymerization temperature is controlled at 65 ± 1 ℃, mean residence time was controlled at 30 minutes, density of hydrogen is controlled at 2%, material directly enters trimerization still D-203, unnecessary propylene enters the first polymeric kettle D-201 through propylene recycle pump P-C3, and control hydrogen is at 4% (v/v) in the gas composition, polymerization temperature is controlled at 80 ℃, pressure-controlling is at 2.0～1.6Mpa, gas composition in the polymeric kettle is by online gas chromatographic detection, after mean residence time is controlled at 30 minutes, polymer material enters the 4th polymeric kettle D-204 and carries out vapour phase polymerization, the control density of hydrogen is at 4.0% (v/v) in the gas composition, polymerization temperature is controlled at 75 ℃, pressure-controlling is at 1.6～1.4Mpa, gas composition in the polymeric kettle is by online gas chromatographic detection, mean residence time was controlled at 30 minutes, emit material, polymer output is 20kg/ hour, dry, add the auxiliary agent granulation, analyze, test the results are shown in Table 1 and table 2.
Embodiment 5.N catalyzer was with 1.0g/ hour, triethyl aluminum and dicyclopentyl dimethoxyl silane are that the ratio of 150mol/10mol/1mol adds the first polymeric kettle D-201 respectively with volume pump in the Al/Si/Ti ratio, adding propylene (per hour add-on 30kg) polymerization temperature simultaneously is controlled at 65 ± 1 ℃ and carries out mass polymerization, stirring velocity is 200 rev/mins, mean residence time is 15 minutes, the D-202 polymerization temperature is controlled at 58 ± 1 ℃, mean residence time was controlled at 30 minutes, take out a small amount of poly-analytical test that carries out from thief hole, see Table 2, the material that comes out from D-202 enters flash tank Q-1, enter propene polymer vapor phase polymerizer D-203, unnecessary propylene enters the reaction of D-201 still through propylene pump after the flash distillation, feed a large amount of hydrogen toward the D-203 still, and control hydrogen is at 12% (v/v) in the gas composition, polymerization temperature is controlled at 80 ℃, pressure-controlling is at 2.0～1.6Mpa, gas composition in the polymeric kettle is by online gas chromatographic detection, after mean residence time is controlled at 30 minutes, polymer material enters D-204 and carries out vapour phase polymerization, control hydrogen is at 10% (v/v) in the gas composition, polymerization temperature is controlled at 75 ℃, pressure-controlling is at 1.6～1.4Mpa, gas composition in the polymeric kettle is by online gas chromatographic detection, mean residence time is emitted material after being controlled at 30 minutes, and polymer output is 20kg/ hour, dry, add the auxiliary agent granulation, analyze, test the results are shown in Table 1 and table 2.
Table 1
Table 2
| Numbering | Number-average molecular weight Mn (ten thousand) | Weight-average molecular weight Mw (ten thousand) | Z-average molecular weight Mz (ten thousand) | Molecular weight distribution breadth index Mn/ |
| 1 30 minutes samples of embodiment | ????37.0 | ????134.6 | ??278.6 | ????3.6 |
| 2 45 minutes samples of embodiment | ????36.0 | ????148.5 | ??348.6 | ????4.1 |
| 45 minutes samples of embodiment 2-1 | ????37.0 | ????158.5 | ??358.8 | ????4.2 |
| 45 minutes samples of embodiment 2-2 | ????35.0 | ????128.5 | ??308.6 | ????3.7 |
| 45 minutes samples of embodiment 2-3 | ????32.0 | ????118.8 | ??298.6 | ????3.7 |
| 3 60 minutes samples of embodiment | ????35.2 | ????145.3 | ??322.7 | ????4.1 |
| Embodiment 4 D-201 samples | ????27.0 | ????132.5 | ??295.8 | ????4.9 |
| Embodiment 4 D-202 samples | ????28.6 | ????140.4 | ??323.5 | ????4.9 |
| Embodiment 5 D-202 samples | ????26.2 | ????141.1 | ??322.3 | ????4.9 |
| Embodiment 3 | ????4.8 | ????84.5 | ??268.9 | ????17.5 |
| Embodiment 2 | ????4.9 | ????60.5 | ??208.9 | ????12.3 |
| | ????4.1 | ????38.5 | ??168.9 | ????9.4 |
| | ????8.0 | ????41.6 | ??109.0 | ????5.2 |
Claims (5)
1. the batch production method of a broad molecular weight distribution polypropylene is characterized in that it is made up of the following step:
A. liquid-phase bulk polymerization: in polymermaking autoclave, add liquid propylene and catalyzer, carry out polymerization at 40～70 ℃, polymerization time 30～90 minutes,
B. vapour phase polymerization: in above-mentioned reaction mixture, feed hydrogen, the volume by volume concentration of hydrogen was 0.5～30%, 70～90 ℃ of polymerizations 60～120 minutes.
2. the continuous production method of a broad molecular weight distribution polypropylene is characterized in that it is made up of the following step:
A. liquid-phase bulk polymerization: in liquid phase polymerizer, add liquid propylene, catalyzer, carry out polymerization at 40～70 ℃, mean residence time is 30～90 minutes in still,
B. flash distillation: A step polymeric material enters a flash tank flash distillation, and temperature is 30～70 ℃, and pressure is 4.5～0.1MPa, and the propylene that flashes off is sent liquid phase polymerizer back to by the propylene recycle pump,
C. fluidized bed gas-phase polymerization: the material after flash distillation carries out vapour phase polymerization, feeds hydrogen, 70～90 ℃ of polymerization temperatures, polymerization 60～120 minutes, H
2Volume by volume concentration is 0.5～30%.
3. the continuous production method of broad molecular weight distribution polypropylene according to claim 2, it is characterized in that: in steps A, two liquid phase polymerizers are arranged, the first liquid phase polymerizer polymerization temperature is controlled at 40～70 ℃, the residence time was controlled at 15～45 minutes, the second reactor polymerization temperature is controlled at 50～70 ℃, and the residence time was controlled at 15～45 minutes, carries out step B flash distillation then.
4. according to the continuous production method of claim 2 or 3 described broad molecular weight distribution polypropylenes, it is characterized in that: in step C, two fluidized bed gas-phase polymerization stills are arranged, the 3rd vapor phase polymerizer pressure-controlling is at 1.0～2.5MPa, and polymerization temperature is controlled at 60～90 ℃, and the residence time was controlled at 15～60 minutes, the hydrogen volume specific concentration is 2～10%, the 4th vapor phase polymerizer pressure-controlling is at 0.8～2.0MPa, and polymerization temperature is controlled at 60～90 ℃, and the hydrogen volume specific concentration is 2～40%.
5. the continuous production method of broad molecular weight distribution polypropylene according to claim 4, it is characterized in that: propylene enters the flash tank flash distillation after the first polymeric kettle polymerization, the propylene that flashes off returns the reaction of first polymeric kettle by the propylene recycle pump, material after the flash distillation enters second polymeric kettle, at 60～75 ℃, the residence time is controlled at carried out liquid-phase bulk polymerization in 15～45 minutes, enter the trimerization still then and carry out vapour phase polymerization, the unnecessary propylene of trimerization still is sent the reaction of second polymeric kettle back to by the propylene recycle pump.
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| CN (1) | CN1259350C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402560C (en) * | 2006-03-08 | 2008-07-16 | 南京金陵塑胶化工有限公司 | Production and reactor for polypropylene |
| CN102822265A (en) * | 2010-02-26 | 2012-12-12 | 博里利斯股份公司 | Random propylene copolymers for pipes |
| CN102050892B (en) * | 2009-10-27 | 2013-03-27 | 中国石油化工股份有限公司 | Method for controlling production of broad-distribution polyolefin |
| CN103360528A (en) * | 2012-03-27 | 2013-10-23 | 中国石油化工股份有限公司 | Preparation method and equipment of high-performance impact polypropylene |
| CN104628912A (en) * | 2015-02-15 | 2015-05-20 | 青岛科技大学 | Preparation methods of polybutylene alloy material |
| CN106432559A (en) * | 2015-08-04 | 2017-02-22 | 山东省滕州瑞达化工有限公司 | Liquid phase synthesis method of high isotactic polybutene-1 |
| CN109810398A (en) * | 2017-11-21 | 2019-05-28 | 中国石油天然气股份有限公司 | A kind of super high molecular weight isotactic polypropylene resin combination and preparation method thereof |
| CN114014963A (en) * | 2021-12-07 | 2022-02-08 | 利和知信新材料技术有限公司 | Method for preparing wide-distribution multiphase polypropylene polymer in gas phase reactor |
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2004
- 2004-03-01 CN CN 200410014194 patent/CN1259350C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402560C (en) * | 2006-03-08 | 2008-07-16 | 南京金陵塑胶化工有限公司 | Production and reactor for polypropylene |
| CN102050892B (en) * | 2009-10-27 | 2013-03-27 | 中国石油化工股份有限公司 | Method for controlling production of broad-distribution polyolefin |
| CN102822265A (en) * | 2010-02-26 | 2012-12-12 | 博里利斯股份公司 | Random propylene copolymers for pipes |
| CN102822265B (en) * | 2010-02-26 | 2014-07-23 | 博里利斯股份公司 | Random propylene copolymers for pipes |
| CN103360528A (en) * | 2012-03-27 | 2013-10-23 | 中国石油化工股份有限公司 | Preparation method and equipment of high-performance impact polypropylene |
| CN103360528B (en) * | 2012-03-27 | 2015-09-16 | 中国石油化工股份有限公司 | A kind of preparation method of high-performance impact polypropylene and equipment |
| CN104628912A (en) * | 2015-02-15 | 2015-05-20 | 青岛科技大学 | Preparation methods of polybutylene alloy material |
| CN104628912B (en) * | 2015-02-15 | 2017-06-20 | 青岛科技大学 | A kind of preparation method of Polybutene alloy material |
| CN106432559A (en) * | 2015-08-04 | 2017-02-22 | 山东省滕州瑞达化工有限公司 | Liquid phase synthesis method of high isotactic polybutene-1 |
| CN106432559B (en) * | 2015-08-04 | 2020-11-17 | 山东省滕州瑞达化工有限公司 | High isotactic polybutene-1 liquid phase synthesis process |
| CN109810398A (en) * | 2017-11-21 | 2019-05-28 | 中国石油天然气股份有限公司 | A kind of super high molecular weight isotactic polypropylene resin combination and preparation method thereof |
| CN114014963A (en) * | 2021-12-07 | 2022-02-08 | 利和知信新材料技术有限公司 | Method for preparing wide-distribution multiphase polypropylene polymer in gas phase reactor |
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| CN1259350C (en) | 2006-06-14 |
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