CN1256352C - Preparation method of transparent high melt strength polypropylene resin - Google Patents
Preparation method of transparent high melt strength polypropylene resin Download PDFInfo
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- CN1256352C CN1256352C CN 200410013826 CN200410013826A CN1256352C CN 1256352 C CN1256352 C CN 1256352C CN 200410013826 CN200410013826 CN 200410013826 CN 200410013826 A CN200410013826 A CN 200410013826A CN 1256352 C CN1256352 C CN 1256352C
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Abstract
The present invention has the goal of providing a method for preparing transparent polypropylene. Polypropylene with ultrahigh molecular weight is generated by polymerization in a liquid-phase bulk polymerization section by a segmental polymerization method and an HYPOL continuous production technology; a new flash tank and a corresponding system thereof are added between a liquid-phase still and a gas-phase still; a chain transfer agent is filled into the liquid-phase polymerization section for polymerization to generate polypropylene with low molecular weight. The polypropylene resin contains a certain amount of polypropylene with ultrahigh molecular weight and has higher melt strength.
Description
Technical field
The present invention relates to a kind of manufacture method of transparent polypropylene resin
Background technology
Polypropylene (PP) is owing to its good performance, the cheap various fields such as trolley part, mechanical part, electrical component, articles for daily use, film for packaging that are widely used in.PP is one of material that is used as the earliest hollow container.Compare with HDPE, the shortcoming of PP maximum be melt easily produce drop down down (melt strength is lower) low temperature resistant poor with impact property, advantage is rigidity and good heat resistance, and density is lower more than 5% than HDPE, for the small-sized beverage packets bottling that requires hot filling, PP has certain performance and price advantage.With the polypropylene blow moulding moulding time, the fused parison is because of easily hanging from body weight, and it is difficult to be shaped, even be shaped, the thickness of its goods is also inhomogeneous, has limited its application aspect blowing, vacuum-thermoform, foaming and molding and large-scale moulded products.The raw material of the situation of present transparent blow-molded article is transparent polyvinyl chloride and PET.Make transparent blow-molded article with polypropylene in the prior art following mode arranged usually:
1) with a spot of new LDPE (film grade) or high density polyethylene(HDPE) and polypropene blended, the acrylic resin of the modification that obtains.
2) make the slight crosslinked modified polypropylene resin of acrylic resin with superoxide, electron beam or toxilic acid etc.;
3) propylene and higher alkene polymerization when polymerization generates the acrylic resin with long-chain branch.
But, adopt the polyacrylic melt strength method of above-mentioned raising, there is certain shortcoming separately, though method 1 and 2 can improve polypropylene fusion intensity, moulded products or outward appearance are ugly, or the transparency descends residual small molecules scent of in the goods.Method 3 higher alkene cost height, and catalyzer had special requirement, the manufacturing cost height.
Publication number CN1141196 manufacture method is to adopt multi-stage polymeric, has made fusion tension force and rigidity height, and the good polypropylene of processability.This method is in the 1st section polymerization, make the limiting viscosity [η] of generation be the 8-13dl/g polypropylene, account for the 15-50% (quality) of whole polymkeric substance, then in the 2nd section polymerization, make the limiting viscosity [η] of generation be the polypropylene about 0.6dl/g, the melt flow rate (MFR) that records during load 2.16kg (MFR) is 0.01～5g/10min; The molecular weight distribution Mw/M that records with gel permeation chromatography is 6～20.This method adopts aq slurry process, needs to make solvent with heptane.
Opening the manufacture method of putting down in writing in the clear 59-172507 communique the spy, is to use the two-phase method polypropylene, obtains all excellent polypropylene such as rigidity, processing characteristics and thermotolerance.This method is that to make limiting viscosity [η] in one section be 1.0～10dl/g, and the isotaxy five-tuple is that the ratio that the above polypropylene of 97.% (quality) accounts for total amount is 35～65 (quality); And make limiting viscosity [η] in another section is that 0.6～1.2dl/g, isotaxy five-tuple are that polypropylene 96.5% (quality) more than accounts for whole polyacrylic 65～35% (quality); Producing whole polyacrylic limiting viscosities [η] is that 1.2～7.0dl/g, molecular weight distribution mw/mn are the polypropylene resin composite of 6-20.
Summary of the invention
The manufacture method that the purpose of this invention is to provide a kind of polypropylene resin composite, this method can be made above-mentioned polypropylene resin composite at an easy rate, simply, effectively.
The object of the present invention is achieved like this:
Adopt existing HYPOL continuous production processes, perhaps batch production technology, polymerization prepares high (superelevation) molecular weight Co-polypropylene stage by stage, with low-molecular-weight Co-polypropylene, contain a certain amount of ethene segment in the polymkeric substance simultaneously, preparation contains a certain amount of high (superelevation) polydispersity polymer, because the existence of ultra-high molecular weight, changed the rheological characteristics of polymer melt, simultaneously in order to satisfy the polymeric rheology performance demands, need a certain amount ofly satisfy melt flowability than small molecular weight, the molecular weight distribution that needs requires broad like this, to the polyacrylic molecular weight distribution mw/mn of the present invention between 8～20, at 230 ℃, record melt flow rate (MFR) at 0.5～5.0g/10min during load 2.16kg, ethylene content is in 0.5～5.0% (quality) in the polymkeric substance.
The HYPOL production technique is the polypropylene production technique of Mitsui oiling exploitation, and its flow process signal can not be satisfied production as Fig. 1 for the ease of produce the existing HYPOL production technique of high molecular weight polypropylene in continuous processing, need do some improvement to Production Flow Chart.
Technical scheme of the present invention is as follows:
A kind of batch process for preparing of transparent polypropylene resin adopts HYPOL technology, and earlier through liquid-phase bulk polymerization, vapour phase polymerization again is characterized in that adopting the following step to carry out polymerization:
A. liquid-phase bulk polymerization: in autoclave, add liquid propylene and catalyzer, feed ethene, the quality of ethene is 0.5～5% than concentration, carry out polymerization at 40～80 ℃, polymerization time 0.5～1.5 hour, its limiting viscosity of the multipolymer of generation is at 5～15dl/g, ethene segmental content is in 0.1～5% (quality)
B. vapour phase polymerization: in above-mentioned reaction mixture, feed hydrogen and ethene, the volume by volume concentration of hydrogen is 2～30%, the quality of ethene is 1～5% than concentration, its limiting viscosity of Co-polypropylene of hour generation is at 0.2～3.5dl/g 60～90 ℃ of polymerase 10 .5～1.5, ethene segmental content is in 1～5% (quality)
The batch process for preparing of above-mentioned transparent polypropylene resin, in steps A, preferred ethene quality is 1～5% than concentration, preferred concentration is 1～3%.
The batch process for preparing of above-mentioned transparent polypropylene resin, in step B, preferred ethene quality is 1～3% than concentration, the volume by volume concentration of hydrogen is 2～25%.
A kind of continuous production method of transparent polypropylene resin adopts HYPOL technology, earlier through liquid-phase bulk polymerization, adopts fluidized bed gas-phase polymerization again, it is characterized in that adopting the following step to carry out polymerization:
A. liquid-phase bulk polymerization: in liquid phase polymerizer, add liquid propylene, catalyzer, feed ethene, the quality of ethene is 0.5～5% than concentration, carry out polymerization at 40～80 ℃, mean residence time is 0.5～1.5 hour in still, and its limiting viscosity of the multipolymer of generation is at 5～15dl/g, ethene segmental content is in 0～5% (quality)
B. flash distillation: A step polymeric material enters a flash tank flash distillation, and temperature 30-70 ℃, pressure 4.5-0.1MPa,
C. fluidized bed gas-phase polymerization: the material after flash distillation carries out vapour phase polymerization, 60～90 ℃ of polymerization temperatures, polymerization time 0.5～1.5 hour, H
2Concentration is 2～30% (V/V), and the second dilute concentration is in 1～5% (quality), and its limiting viscosity of the Co-polypropylene of generation is at 0.2～3.5dl/g, and ethene segmental content is in 1～5% (quality).
The continuous production method of above-mentioned transparent polypropylene resin, in steps A, two liquid phase polymerizers can be arranged, the first liquid phase polymerizer polymerization temperature is controlled at 45～80 ℃, the residence time was controlled at 15～30 minutes, the second reactor polymerization temperature is controlled at 40～75 ℃, and the residence time was controlled at 15～60 minutes.
The continuous production method of above-mentioned transparent polypropylene resin, in step C, two fluidized bed gas-phase polymerization stills can be arranged, the 3rd vapor phase polymerizer pressure-controlling is at 2.0～1.6MPa, polymerization temperature is controlled at 60～90 ℃, the residence time was controlled at 15～30 minutes, the hydrogen volume specific concentration is 2～10%, the ethene quality is 3～5% than concentration, the 4th vapor phase polymerizer pressure-controlling is at 1.6～1.4MPa, polymerization temperature is controlled at 60～90 ℃, and the hydrogen volume specific concentration is 10～30%, and the ethene quality is 1～3% than concentration.
With the melt flow rate (MFR) of polymkeric substance polymkeric substance under 230 ℃ of 10kg loads of this law preparation at 0.01～3.0g/10min.
Polymkeric substance adds oxidation inhibitor, thermo-stabilizer, halogen-absorber, nucleator mixing back melt pelletization after drying.
This acrylic resin has higher melt strength, high impulse strength, high transparent, can be at the various goods of the interval blowing of wider processing temperature, and be fit to carry out blowing, PP blowing is with used comparing on raw material and the present market, toughness, low-temperature performance have bigger improvement, and the bottle breakage rate is little during production, and the ratio of performance to price more has superiority; Compare with HDPE, use PP has not only improved the thermotolerance and the dimensional stability of beverage bottle, and because PP density is little, and the materials amount is few, and price is also cheap than HDPE, economic benefit is very remarkable.
Adopt method of the present invention, Co-polypropylene has wider molecular weight distribution, and contain more high molecular weight polypropylene, high molecular partly accounts for polypropylene in 10～40% (quality), molecular weight distribution mw/mn is 6～20, and its limiting viscosity of Co-polypropylene is at 0.2～3.5dl/g, and high-quality product is at 1.0～2.5dl/g, the melt flow rate (MFR) of polymkeric substance is at 0.5～5.0g/10min under 230 ℃ of 10kg load, high-quality product 1.0～3.0g/10min.This polypropylene has higher melt strength, the height of fusion ratio reflects the variation of melt strength, fusion is than the polyacrylic melt strength height of high explanation, with the fusion of the Co-polypropylene of prior art than between 10～20, the fusion of adopting the Co-polypropylene that the present invention produces than MFR10/MFR2.16 between 25～35.
Description of drawings
Fig. 1 improves the polyacrylic HYPOL technological process of production synoptic diagram in back, 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, and Q-1 is newly-increased flash tank.
Embodiment
In following examples:
The test of transparent polypropylene resin batch process for preparing is carried out at the 10L polymermaking autoclave, and the transparent polypropylene resin continuous production method is carried out the continuous production test on the HYPOL processing unit after the improvement.
The batch process for preparing aggregation test carries out on 10L polymermaking autoclave testing apparatus, polymeric kettle with nitrogen purging after, extract polymeric kettle gas out with vacuum pump.Catalyzer, triethyl aluminum, dicyclopentyl dimethoxyl silane etc. join under nitrogen protection in the catalyzer feeder, and the liquid propene jar adds polymeric kettle with propylene after the surge pump pressurization, and propylene measures with electronic balance.The hydrogen pressure pan with the pressure difference metering, enters reactor, and ethene feeds polymeric kettle via mass-flow gas meter, 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, and behind the polymerization certain hour, the gas composition in the polymeric kettle is by online gas chromatographic detection, emit material by baiting valve behind the polymerization certain hour, dry, weigh, add nucleator and other auxiliary agent, carry out granulation with the twin screw extruder group, analyze.
Long run test adopts the experiment process of Fig. 1, with fresh propylene, ethene, catalyzer, triethyl aluminum, dicyclopentyl dimethoxyl silane etc. add 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.
Limiting viscosity, testing standard is pressed GB/T1841-80, and testing tool is Dutch TAMSON, makees solvent with perhydronaphthalene, calculates with the extrapotation test, and viscosity-average molecular weight adopts following formula to calculate [η]=K
ηM
η αK wherein
η=7.4*10
-4Dl/g, α=0.64.
Embodiment 1. discontinuous methods prepare transparent polypropylene resin
Z-N catalyst n type, Ti content is in 2.0%.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 Z-N N type catalyzer 60.0mg, triethyl aluminium solution 3.0ml, dicyclopentyl dimethoxyl silane solution 1.5ml join in the catalyzer feeder under nitrogen protection.In polymermaking autoclave, add propylene 2500g., ethene feeds with 25g/ hour speed, be rapidly heated, temperature is controlled at 65 ± 1 ℃ and carries out mass polymerization, stirring velocity is 200 rev/mins, in polymerization in the time of 60 minutes, get the copolymerized polymer sample a little, carry out the limiting viscosity analysis of polymkeric substance after the drying, see Table 1, feed hydrogen 10L, 1.22L ethene, polymerization temperature is controlled at 75 ± 5 ℃, gas composition in the polymeric kettle is by online gas chromatographic detection, and polymerization was emitted material by baiting valve, drying in 60 minutes, weigh, get polymkeric substance 2248g, add nucleator and other auxiliary agent granulation, analyze, it the results are shown in Table 1, table 2.
Embodiment 2. discontinuous methods prepare transparent polypropylene resin
Catalyst system is with embodiment 1, accurate weighing N type catalyzer 60.0mg, and triethyl aluminium solution 3.0ml, dicyclopentyl dimethoxyl silane solution 2.0ml join in the catalyzer feeder under nitrogen protection.In polymermaking autoclave, add propylene 2500g, be rapidly heated, ethene feeds with 25g/ hour speed, temperature is controlled at 65 ± 1 ℃ and carries out mass polymerization, stirring velocity is 200 rev/mins, in polymerization in the time of 60 minutes, get the copolymerized polymer sample a little, carry out the limiting viscosity analytical test of polymkeric substance after the drying, see Table 1, feed hydrogen 30L, ethene 1.62L polymerization temperature is controlled at 75 ± 5 ℃, gas composition in the polymeric kettle is by online gas chromatographic detection, polymerization was emitted material by baiting valve, drying in 60 minutes, weigh, get polymkeric substance 2380g, add nucleator and other auxiliary agent granulation, analyze, it the results are shown in Table 1, table 2.
Contrast experiment's 1. one-stage processes prepare polypropylene
Catalyst system is with embodiment 1, accurate weighing N type catalyzer 60.0mg, and triethyl aluminium solution 3.0ml, dicyclopentyl dimethoxyl silane solution 2.0ml join in the catalyzer feeder under nitrogen protection.In polymermaking autoclave, add propylene 2500g, ethene feeds with 25g/ hour speed, feeds hydrogen 10L, is rapidly heated, temperature is controlled at 70 ± 1 ℃ and carries out mass polymerization, stirring velocity is 200 rev/mins, in the time of 120 minutes, emits material by baiting valve in polymerization, dry, weigh, polymkeric substance 2100g, add nucleator and other auxiliary agent granulation, analyze, it the results are shown in Table 1, table 2.
Transparent polypropylene resin takes place to produce in embodiment 3. continuous production
Catalyst system is with embodiment 1, N type catalyzer was with 1.0g/ hour, triethyl aluminum and dicyclopentyl dimethoxyl silane are that the ratio of 100mol/10mol/1mol adds the D-201 still respectively with volume pump in the Al/Si/Ti ratio, polymerization temperature is controlled at 68 ± 1 ℃ and carries out mass polymerization, and feeding ethene, and the ethylene gas phase concentration is controlled at 1-2% (quality), stirring velocity is 200 rev/mins, mean residence time was at 15 minutes, from carrying out the limiting viscosity analytical test of polymkeric substance after thief hole takes out a small amount of polypropylene drying, see Table 2, D-202 still polymerization temperature is controlled at 63 ± 1 ℃, the ethylene gas phase concentration is controlled at 1-2% (quality), mean residence time was controlled at 30 minutes, take out a small amount of polypropylene from thief hole and carry out the limiting viscosity analytical test, see Table 2, material enters the Q-1 flash tank, unnecessary propylene and ethene enter the D-201 still through pump P-C3, propene polymer enters vapor phase polymerizer D-203, feed a large amount of hydrogen, and control hydrogen is at 2% (v/v) in the gas composition, the ethylene gas phase concentration is controlled at 4-5% (quality), polymerization temperature is controlled at 75 ℃, 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 D-204 still and carries out vapour phase polymerization, and control hydrogen is at 10% (v/v) in the gas composition, and the ethylene gas phase concentration is controlled at 2-3% (quality), polymerization temperature is controlled at 75 ℃, pressure-controlling is at 1.6～1.4Mpa, and the gas composition in the polymeric kettle is by online gas chromatographic detection, after mean residence time is controlled at 45 minutes, emit material, polymer output is 20kg/ hour, drying, add nucleator and other auxiliary agent granulation, analyze.
Embodiment 4, catalyst system is with embodiment 1, N type catalyzer was with 1.0g/ hour, triethyl aluminum and dicyclopentyl dimethoxyl silane are that the ratio of 100mol/10mol/1mol adds the D-201 still respectively with volume pump in the Al/Si/Ti ratio, polymerization temperature is controlled at 68 ± 1 ℃ and carries out mass polymerization, and feeding ethene, and the ethylene gas phase concentration is controlled at 4-5% (quality), stirring velocity is 200 rev/mins, mean residence time was at 80 minutes, from carrying out the limiting viscosity analytical test of polymkeric substance after thief hole takes out a small amount of polypropylene drying, see Table 2, D-202 still polymerization temperature is controlled at 63 ± 1 ℃, the ethylene gas phase concentration is controlled at 1-2% (quality), mean residence time was controlled at 30 minutes, take out a small amount of polypropylene from thief hole and carry out the limiting viscosity analytical test, see Table 2, material enters the Q-1 flash tank, unnecessary propylene and ethene enter the D-201 still through pump P-C3, propene polymer enters vapor phase polymerizer D-203, feed a large amount of hydrogen, and control hydrogen is at 12% (v/v) in the gas composition, the ethylene gas phase concentration is controlled at 2-3% (quality), polymerization temperature is controlled at 75 ℃, pressure-controlling is at 2.0～1.6Mpa, gas composition in the polymeric kettle is by online gas chromatographic detection, and after mean residence time was controlled at 30 minutes, polymer material entered the D-204 still and carries out vapour phase polymerization, control hydrogen is at 10% (v/v) in the gas composition, the ethylene gas phase concentration is controlled at 2-3% (quality), and polymerization temperature is controlled at 75 ℃, and 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 45 minutes, and polymer output is 20kg/ hour, dry, add nucleator and other auxiliary agent granulation, analyze.
The contrast experiment 2, N type catalyzer was with flow 1.0g/ hour, triethyl aluminum and dicyclopentyl dimethoxyl silane are that the ratio of 100mol/10mol/1mol adds the D-201 still respectively with volume pump in the Al/Si/Ti ratio, polymerization temperature is controlled at 68 ± 1 ℃ and carries out mass polymerization, density of hydrogen is controlled at 2% (V/V), the ethylene gas phase concentration is controlled at 2-3% (quality), stirring velocity is 200 rev/mins, mean residence time was at 15 minutes, the D-202 polymerization temperature is controlled at 65 ± 1 ℃, mean residence time was controlled at 30 minutes, density of hydrogen is controlled at 2% (V/V), material directly enters the D-203 still, unnecessary propylene, ethene and hydrogen enter the D-201 still through pump P-C3, and control hydrogen is at 4% (v/v) in the gas composition, the ethylene gas phase concentration is controlled at 4% (quality), polymerization temperature is controlled at 70 ℃, 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 D-204 still and carries out vapour phase polymerization, the control density of hydrogen is at 4.0% (v/v) in the gas composition, the ethylene gas phase concentration is controlled at 4% (quality), polymerization temperature is controlled at 75 ℃, pressure-controlling is at 1.6～1.4Mpa, and the gas composition in the polymeric kettle is by online gas chromatographic detection, after mean residence time is controlled at 30 minutes, emit material, polymer output is 20kg/ hour, dry, add nucleator and other auxiliary agent granulation, analyze, the results are shown in Table 1.
The polyacrylic performance of table 1
Table 2
| Numbering | Limiting viscosity η dl/g | Melt body flow rate MFR (lotus .16kg) | Melt body flow rate MFR (load 10.0kg) | Molten ratio | Ethylene content % (quality) |
| 1 60 minutes samples of embodiment | 11.0 | ＜0.1 | 0.2 | --- | 2.5 |
| Embodiment 1 | 3.8 | 1.2 | 36.2 | 30.2 | 2.9 |
| 2 60 minutes samples of embodiment | 10.3 | ＜0.1 | 0.31 | --- | 2.7 |
| Embodiment 2 | 2.5 | 2.2 | 70.0 | 31.8 | 3.1 |
| Embodiment 3 D-201 samples | 8.9 | ＜0.1 | 0.38 | 4.9 | 2.1 |
| Embodiment 3 D-202 samples | 9.8 | ＜0.1 | 0.35 | 4.9 | 2.4 |
| Embodiment 3 | 3.4 | 1.20 | 40.5 | 33.8 | 3.1 |
| Simultaneous test 2 D-201 samples | 3.4 | 0.8 | 16.1 | 4.9 | 3.0 |
| Simultaneous test 2 D-202 samples | 3.5 | 0.7 | 12.3 | 4.9 | 3.1 |
| Simultaneous test 1 | 2.9 | 1.1 | 16.0 | 14.5 | 3.4 |
| Simultaneous test 3 | 3.2 | 1.5 | 21.9 | 14.6 | 3.2 |
The polypropylene of the polypropylene of embodiment 3 and simultaneous test 2 carries out the blowing test respectively, and test is carried out on blow moulding machine, the container of blowing 1 and 5L, and test-results is as follows:
| The 1L container blowing | The 5L container blowing | |||
| Embodiment 3 | Simultaneous test 2 | Embodiment 3 | Simultaneous test 2 | |
| Blow molding difficulty products appearance transparency goods thickness | Good easily even | Difficult difference is generally inhomogeneous | Even carefully easily | Be difficult to moulding-------- |
The blowing test-results shows the polypropylene that adopts the present invention's preparation, not only can satisfy the requirement that small hollow is held blow molding, and the requirement of bigger medium-sized hollow container blow molding in satisfying.
Claims (7)
1. the batch process for preparing of a transparent polypropylene resin adopts HYPOL technology, and earlier through liquid-phase bulk polymerization, vapour phase polymerization again is characterized in that adopting the following step to carry out polymerization:
A. liquid-phase bulk polymerization: in autoclave, add liquid propylene and catalyzer, feed ethene, the quality of ethene is 0.5～5% than concentration, carry out polymerization at 40～80 ℃, polymerization time 0.5～1.5 hour, its limiting viscosity of the multipolymer of generation is at 5～15dl/g, ethene segmental quality percentage composition is 0.1～5%
B. vapour phase polymerization: in above-mentioned reaction mixture, feed hydrogen and ethene, the volume by volume concentration of hydrogen is 2～30%, the quality of ethene is 1～5% than concentration, its limiting viscosity of Co-polypropylene of hour generation is at 0.2～3.5dl/g 60～90 ℃ of polymerase 10 .5～1.5, ethene segmental content is in 1～5% (quality)
2. the batch process for preparing of transparent polypropylene resin according to claim 1, it is characterized in that: in steps A, the ethene quality is 1～5% than concentration,
3. the batch process for preparing of transparent polypropylene resin according to claim 1, it is characterized in that: in steps A, the ethene quality is 1～3% than concentration.
4. the batch process for preparing of transparent polypropylene resin according to claim 1, it is characterized in that: in step B, the ethene quality is 1～3% than concentration, and the volume by volume concentration of hydrogen is 2～25%.
5. the continuous production method of a transparent polypropylene resin adopts HYPOL technology, earlier through liquid-phase bulk polymerization, adopts fluidized bed gas-phase polymerization again, it is characterized in that adopting the following step to carry out polymerization:
A. liquid-phase bulk polymerization: in liquid phase polymerizer, add liquid propylene, catalyzer, feed ethene, the quality of ethene is 0.5～5% than concentration, carry out polymerization at 40～80 ℃, mean residence time is 0.5～1.5 hour in still, and its limiting viscosity of the multipolymer of generation is at 5～15dl/g, ethene segmental quality percentage composition is 0.1～5%
B. flash distillation: A step polymeric material enters a flash tank flash distillation, and temperature 30-70 ℃, pressure 4.5-0.1MPa,
C. fluidized bed gas-phase polymerization: the material after flash distillation enters vapor phase polymerizer and carries out vapour phase polymerization, 60～90 ℃ of polymerization temperatures, and mean residence time is 0.5～1.5 hour in polymeric kettle, H
2Volume by volume concentration is 2～30%, and the ethene mass percentage concentration is 1～5%.
6. the continuous production method of transparent polypropylene resin according to claim 5, it is characterized in that: in steps A, two liquid phase polymerizers can be arranged, the first liquid phase polymerizer polymerization temperature is controlled at 45～80 ℃, the residence time was controlled at 15～30 minutes, the second reactor polymerization temperature is controlled at 40～75 ℃, and the residence time was controlled at 15～60 minutes.
7. the continuous production method of transparent polypropylene resin according to claim 5, it is characterized in that: in step C, two fluidized bed gas-phase polymerization stills can be arranged, the 3rd vapor phase polymerizer pressure-controlling is at 2.0～1.6MPa, polymerization temperature is controlled at 60～90 ℃, the residence time was controlled at 15～30 minutes, the hydrogen volume specific concentration is 2～10%, the ethene quality is 3～5% than concentration, the 4th vapor phase polymerizer pressure-controlling is at 1.6～1.4MPa, polymerization temperature is controlled at 60～90 ℃, and the hydrogen volume specific concentration is 10～30%, and the ethene quality is 1～3% than concentration.
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