CN103254342B - For the manufacture of the preparation method of the bimodal Linear low-density polyethylene composition of film - Google Patents
For the manufacture of the preparation method of the bimodal Linear low-density polyethylene composition of film Download PDFInfo
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- CN103254342B CN103254342B CN201210037722.5A CN201210037722A CN103254342B CN 103254342 B CN103254342 B CN 103254342B CN 201210037722 A CN201210037722 A CN 201210037722A CN 103254342 B CN103254342 B CN 103254342B
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Abstract
The present invention relates to a kind of preparation method of the bimodal Linear low-density polyethylene composition for the production of film.Bimodal Linear low-density polyethylene composition prepared by the method, its low-molecular weight polymer content is 40 ~ 50wt%, and high-molecular weight polymer content is 50 ~ 60wt%; The melt flow rate (MFR) of this bimodal Linear low-density polyethylene composition is 0.6 ~ 1.4g/10min, and density is 0.910 ~ 0.920g/cm
3; This bimodal Linear low-density polyethylene composition oligomer is low, has the mechanical property of excellent machinability and improvement.The method preparation process to catalyzer and carrier media not high, technique is simple and with low cost.
Description
Technical field
The present invention relates to polymeric film field.Specifically, the present invention relates to a kind of preparation method of the bimodal Linear low-density polyethylene composition for the manufacture of film.
Background technology
Due to bimodal distribution polyethylene can under many extreme conditions the processing characteristics (low molecular weight part) of balancing material and use properties (high molecular weight moieties), become the important directions of polyolefin synthetic resin high performance at present.Be known in the art many methods being used for producing bimodal polyethylene.Known being used for of technique comprising two or more series connection annular tube type or tank reactor produces the homogeneous polyethylene material in end-use with excellent machinability.But the limitation of these techniques only can produce to have relative high density higher than about 0.935g/cm
3bimodal polyethylene.On the other hand, comprising the technique using the technique of two or more series connection Gas-phase reactor and use annular tube type and the Gas-phase reactor of connecting also is known in the art.The advantage of these techniques to produce the bimodal polyethylene of wide density range.
The production method of bimodal polyethylene mainly contains melt blend, step reaction method and one section of reaction method 3 kinds.Adopt stepwise process production bimodal polyethylene, especially when the first polymerization stage produces low-molecular weight polymer, a typical problem is the formation that molecular weight is less than the oligopolymer of 10,000.Molecular weight is intensity and the rigidity that hundreds of, thousands of oligopolymer not only affects product, also can produce smell and smog man-hour adding, make product with peculiar smell, the oligopolymer that especially molecular weight is less than 3000 easily dissolves in a solvent, easily causes last handling process generation plugging.Have been found that the existence having oligopolymer in the polymer sample after the first polymerization stage.Also have been found that the content of oligopolymer with in reactor to produce the MFR of polymkeric substance relevant, when MFR increases, the content of oligopolymer also increases.
CN1325528C discloses a kind of method being suitable for the bimodal LLDPE material of manufacture of film application target, and be included in ethene and alpha-olefin comonomer in loop reactor and carry out copolymerization, production one has melt flow rate (MFR) MFR
2be 50 ~ 500g/10min and density be 0.945 ~ 0.953g/cm
3low-molecular weight polymer.This polyreaction proceeds to produce a kind of high-molecular weight polymer in Gas-phase reactor, thus makes final polymer composition have required performance, the melt flow rate (MFR) MFR of gained bimodal polymer
2be 0.4 ~ 1.0g/10min and density be 0.918 ~ 0.925g/cm
3.The method reduces fine powder (i.e. oligopolymer) in polymkeric substance by selecting suitable catalyst support material, and require higher to support of the catalyst, reaction process is complicated, and cost is higher.
Therefore, it is low that current needs research and development one can obtain oligomer, has the bimodal polyethylene composition of the mechanical property of excellent machinability and improvement, and its preparation process to catalyzer and carrier media not high, technique is simple, bimodal polyethylene composition technology of preparing with low cost.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, provides a kind of method of the bimodal Linear low-density polyethylene composition for the production of film.The bimodal Linear low-density polyethylene composition oligomer that the method is produced is low, there is the bimodal polyethylene composition of the mechanical property of excellent machinability and improvement, and its preparation process to catalyzer and carrier media not high, technique is simple, bimodal polyethylene composition technology of preparing with low cost.
For this reason, the invention provides a kind of preparation method of the bimodal Linear low-density polyethylene composition for the manufacture of film, comprising:
Steps A, ethene, hydrogen and comonomer carry out slurry polymerization and obtain low-molecular ethylene polymers slurries under polymerizing catalyst existence condition;
Step B, low-molecular weight polymer slurries obtain low-molecular ethylene polymers crude product through flash separation ethene and hydrogen;
Step C, carries out centrifugation and filtration treatment to low-molecular weight polymer crude product, obtained low-molecular ethylene polymers;
Step D, ethene, comonomer, hydrogen and low-molecular ethylene polymers carry out gas phase polymerization under polymerizing catalyst existence condition, obtained high molecular weight ethylene copolymer;
Step e, low-molecular ethylene polymers and high molecular weight ethylene copolymer mixing, obtained bimodal Linear low-density polyethylene composition;
Wherein, centrifugal separation processes described in step C is carried out in the whizzer of spray washing, and solvent for use is hexane, and solvent load is 1.5 times of filter cake volume, and the temperature of centrifugal treating process is 55 ~ 65 DEG C.
In a preferred embodiment of the invention, the temperature of the process of centrifugal treating described in step C is 60 DEG C, and pressure is the reaction pressure being not less than Gas-phase reactor.
Bimodal Linear low-density polyethylene composition for the manufacture of film of the present invention is by the reactor that formed of at least being connected by the first polymerization reactor and the second polymerization reactor, by ethene at lower pressures and carry out under polymerizing catalyst existence condition being polymerized or the incompatible manufacture of copolymerization, in the present invention, at least the first polymerization reactor stirs slot type slurry-phase reactor, and at least the second polymerization reactor is Gas-phase reactor.
According to the inventive method, in steps A, by ethene, comonomer and hydrogen feed to the first polymerization reactor, the condition of stirred tank reactor is selected to be polymerized in stirred tank reactor to make 40 ~ 50% weight in whole product, preferably 45 ~ 50% weight.Polymeric reaction temperature is 80 ~ 90 DEG C, and pressure is 0.2 ~ 1.0MPa; Preferred polymeric temperature of reaction is 82 ~ 86 DEG C, and pressure is 0.4 ~ 0.8MPa.
In above-mentioned charging, hydrogen effect is as molecular weight regulator, and the amount of hydrogen depends on the molecular weight needed for this polymkeric substance, and hydrogen and ethene mol ratio in the gas phase depend on the melt flow rate (MFR) needed for polymkeric substance to be prepared; The alpha-olefin comonomer added and the ratio of ethene depend on density polymer obtained in first step.
In one embodiment of the invention, comonomer described in steps A is C4 ~ 10 alpha-olefin, and its inlet amount is 20 ~ 40g/kg ethene; Described hydrogen and ethene mol ratio is in the gas phase 4.0 ~ 12.0.Preferred described comonomer is 1-octene, and described hydrogen and ethene mol ratio is in the gas phase 5 ~ 10.Comonomer described in steps A is C4 ~ 10 alpha-olefin, and its inlet amount is 5 ~ 50g/kg.
According to the inventive method, polymerizing catalyst described in steps A is Ziegler-natta catalyst, and its consumption is 0.2g/kg ethene.Polymerizing catalyst described in steps A particularly preferably in wide hydrogen/volume of ethylene than the catalyzer in scope with high general activity and good active balance.As an example, BCE catalyzer can be adopted.In order to improve catalyst activity further, in polymerization process of the present invention, also need to add promotor, described promotor is triethyl aluminum.Polyreaction solvent for use is hexane, and will be fed to separately in the first polymerization reactor after catalyzer and the dilution of promotor hexane, the product that polymerization obtains by stirring suspension in a solvent.
In one embodiment of the invention, polymerization reaction heat is removed by the water coolant in the vaporization heat of solvent hexane and reactor jacket.The residence time in slurry-phase reactor is 1.0 ~ 4.0h, is preferably 1.5 ~ 3.0h, to obtain enough polyreaction degree.
In order to desolvation and dissolving oligopolymer are in a solvent to reduce plugging problem during conveying, between reactor, usually need separating step, this separating step carries out usually under the pressure lower than the first polymerization procedure.
According to the inventive method, after slurry polymerization, the slurries of the low-molecular weight polymer that steps A obtains by step B enter flash tank by overflow manner, after the flash distillation most of unreacted ethene of removing and hydrogen, by obtained low-molecular weight polymer crude product, with being pumped into desolvation and dissolving oligopolymer in a solvent in whizzer.
In an embodiment of the inventive method, the melt flow rate (MFR) MFR of low-molecular weight polymer described in step C
2be 50 ~ 1000g/10min, density is 0.920 ~ 0.940g/cm
3.The melt flow rate (MFR) MFR of preferred described low-molecular weight polymer
2be 400 ~ 800g/10min, density is 0.925 ~ 0.935g/cm
3.
According to the inventive method, the low-molecular ethylene polymers after centrifugation and filtration treatment desolvation and oligopolymer enters the second polymerization reactor by worm conveyor.This reactor is Gas-phase reactor, and ethene wherein, comonomer and hydrogen are polymerized in gas reaction medium and under polymerizing catalyst existence.This Gas-phase reactor is preferably a kind of horizontal type agitated bed reactor, in horizontal type agitated bed reactor, gaseous fraction enters from reactor bottom, and this bed is remained on sub-fluidized state, reaction heat is removed by the quench liquid sprayed into from reactor head, and quench liquid can be selected from C
6-8inertia alkane, preferred normal hexane.
In one embodiment of the invention, the temperature of reaction in gas phase polymerization apparatus is 70 ~ 90 DEG C, and pressure is 0.1 ~ 0.5MPa; Preferable reaction temperature is 75 ~ 80 DEG C, and pressure is 0.15 ~ 0.3MPa.
According to the inventive method, be 40% ~ 60% of two sections of total add-ons of ethene in vapour phase polymerization section ethene add-on.The ratio controlling comonomer and the ethene added in Gas-phase reactor has desired density to make final polymer composition; Hydrogen/the ethylene molar ratio controlled in Gas-phase reactor makes final polymer composition have desired melt flow rate (MFR).
According in an embodiment of the inventive method, comonomer described in step D is C4 ~ 10 alpha-olefin, and its inlet amount is 100 ~ 150g/kg ethene; Described hydrogen and ethene mol ratio is in the gas phase 0.001 ~ 0.2.Preferred described comonomer is 1-octene, and described hydrogen and ethene mol ratio is in the gas phase 0.01 ~ 0.1.
In another embodiment of the method in accordance with the present invention, the residence time of polymkeric substance in Gas-phase reactor is 0.5 ~ 2.5h, is preferably 1.0 ~ 2.0h.
According to the present invention, because the catalyzer added in steps A also has active, vapour phase polymerization can be proceeded.So the catalyzer in steps A still can be continued to use in the polymerization process of step D, without the need to adding live catalyst.
In one embodiment of the invention, described in step e, bimodal Linear low-density polyethylene composition comprises low-molecular ethylene polymers and high molecular weight ethylene copolymer, wherein, low-molecular ethylene polymers content is 40 ~ 50wt%, and the content of high molecular weight ethylene copolymer is 60 ~ 50wt%; The melt flow rate (MFR) MFR of described composition
2be 0.6 ~ 1.4g/10min, density is 0.910 ~ 0.920g/cm
3.The melt flow rate (MFR) MFR of preferred described composition
2be 0.8 ~ 1.2g/10min, density is 0.910 ~ 0.920g/cm
3.
The mensuration of above-mentioned melt flow rate (MFR), is according to ISO 1133, carries out at 190 DEG C.Wherein load is expressed as subscript, such as, and MFR
2measure at 2.16 kg load.
The mensuration of above-mentioned density, carries out according to ISO 1183.
The mensuration of above-mentioned tensile property, carries out according to ISO 527-3.
Bimodal Linear low-density polyethylene composition for the manufacture of film of the present invention is by the reactor system at least formed by the first reactor and the second reactors in series by vinyl polymerization or the incompatible manufacture of copolymerization.According to the reactor system of the inventive method except the first reactor and the second reactor, other reactor can also be comprised.
In a preferred embodiment of the inventive method, the reactor for prepolymerization before the first reactor, may be comprised; Or also can any one be divided into two or more reactor by the first or second reactor.
In a specific embodiment of the present invention, in pre-polymerization process, whole catalyzer is loaded in stirred tank reactor, and prepolymerization is carried out in slurry polymerization mode.This prepolymerization obtains larger particle in subsequent reactor, finally obtain evenly product.
The present invention can produce the low molecular weight polyethylene of high melt flow rate (MFR), particularly MFR by stirred-tank reactor
2be greater than the low molecular weight polyethylene of 500, make material have good processing characteristics; By whizzer desolvation and dissolving oligopolymer in a solvent, reducing the plugging problem of polymkeric substance when carrying, being also conducive to follow-up gas-phase polymerization processes, production process can be carried out for a long time.Composition obtained thus has processing characteristics and the mechanical property of improvement.
It should be noted that, the feature of Linear low-density polyethylene composition of the present invention is not limited to any one above-mentioned independent feature, but comprises above-mentioned all features.By the combination of features of this uniqueness, can obtain having the film, particularly processing characteristics of premium properties, tensile strength, resistance to rapid crack propagation, stretching yield stress and resistance to slow crack expansibility.
Embodiment
Describe the present invention in detail below in conjunction with embodiment, these embodiments only play illustrative effect, are not limited to range of application of the present invention.
Embodiment
Example 1:
Rear for the dilution of BCE catalyzer solvent hexane and triethyl aluminum catalyst, solvent hexane are joined in the first reactor stirred-tank reactor of 100L from catalyst inlet and colvent inlet respectively, adds the mixture of ethene, hydrogen and 1-octene simultaneously from feed(raw material)inlet.The polymerizing condition of the first reactor and the performance of polymerization product are listed in Table 1.
After slurry polymerization completes, the slurries containing polymkeric substance are introduced in flash tank, at this separating ethene and hydrogen by the overflow port on reactor.Slurries after flash distillation desolvation hexane in the whizzer be pumped into spray washing and dissolving oligopolymer in hexane, washing solvent for use is hexane, and solvent load is 1.5 times of filter cake volume.The service temperature of flash tank is 60 DEG C, and pressure is 0.01MPa, and service temperature and the pressure of whizzer are listed in Table 1.
The polymkeric substance of desolvation is introduced in the second reactor horizontal type agitated bed reactor through worm conveyor, additional ethene, a small amount of hydrogen and 1-octene are introduced from reactor bottom, sprays into quench liquid hexane from the top of Gas-phase reactor constant to maintain temperature of reaction simultaneously.The polymerizing condition of the second reactor and the performance of the finished product are also listed in Table 1.
Embodiment 2:
Repeat the step of embodiment 1, the characteristic of polymerizing condition and resulting polymers is also listed in Table 1.
Embodiment 3:
Repeat the step of embodiment 1, the characteristic of polymerizing condition and resulting polymers is also listed in Table 1.
Embodiment 4:
Repeat the step of embodiment 1, the characteristic of polymerizing condition and resulting polymers is also listed in Table 1.
Embodiment 5:
Repeat the step of embodiment 1, the characteristic of polymerizing condition and resulting polymers is also listed in Table 1.
Embodiment 6:
Repeat the step of embodiment 1, the characteristic of polymerizing condition and resulting polymers is also listed in Table 1.
Comparative example 1:
A kind of bimodal LLDPE is produced in factory.Adopt Loop Slurry and gas-phase fluidized-bed series connection method, the characteristic of polymerizing condition and resulting polymers also can obtain in Table 1.
Table 1
As can be seen from above-described embodiment and comparative example, compared with comparative example, the Linear low-density polyethylene composition obtained according to the inventive method has larger tensile strength, resistance to rapid crack propagation, stretching yield stress and resistance to slow crack expansibility.
Claims (7)
1., for the manufacture of a preparation method for the bimodal Linear low-density polyethylene composition of film, comprising:
Steps A, ethene, hydrogen and comonomer carry out slurry polymerization and obtain low-molecular ethylene polymers slurries under polymerizing catalyst existence condition in stirring slot type slurry-phase reactor;
Step B, low-molecular weight polymer slurries obtain low-molecular ethylene polymers crude product through flash distillation;
Step C, carries out centrifugation and filtration treatment to low-molecular weight polymer crude product, obtained low-molecular ethylene polymers;
Step D, ethene, comonomer, hydrogen and low-molecular ethylene polymers carry out gas phase polymerization under polymerizing catalyst existence condition in horizontal type agitated bed reactor, obtained high molecular weight ethylene copolymer;
Step e, low-molecular ethylene polymers and high molecular weight ethylene copolymer mixing, obtained bimodal Linear low-density polyethylene composition;
Wherein, centrifugal separation processes described in step C is carried out in the whizzer of spray washing, and solvent for use is hexane, and solvent load is 1.5 times of filter cake volume, and the temperature of centrifugal treating process is 55 ~ 65 DEG C;
The MFR of low-molecular weight polymer described in step C
2be 400 ~ 800g/10min, density is 0.925 ~ 0.935g/cm
3;
In step e, the MFR of described bimodal Linear low-density polyethylene composition
2be 0.8 ~ 1.2g/10min, density is 0.912 ~ 0.918g/cm
3.
2. method according to claim 1, is characterized in that, the temperature of the process of centrifugal treating described in step C is 60 DEG C, and pressure is the reaction pressure being not less than Gas-phase reactor.
3. method according to claim 1, is characterized in that: comonomer described in steps A is selected from one or more in the alpha-olefin of C4 ~ 10, and its inlet amount is 20 ~ 40g/kg ethene; Described hydrogen and ethene mol ratio is in the gas phase 4.0 ~ 12.0.
4. method according to claim 3, is characterized in that: comonomer described in steps A is 1-octene, and described hydrogen and ethene mol ratio is in the gas phase 5 ~ 10.
5. method according to claim 1, is characterized in that: comonomer described in step D is one or more in the alpha-olefin of C4 ~ 10, and its inlet amount is 100 ~ 150g/kg ethene; Described hydrogen and ethene mol ratio is in the gas phase 0.001 ~ 0.2.
6. method according to claim 5, is characterized in that: described comonomer is 1-octene, and described hydrogen and ethene mol ratio is in the gas phase 0.01 ~ 0.1.
7. method according to claim 1, it is characterized in that: described in step e, bimodal Linear low-density polyethylene composition comprises low-molecular ethylene polymers and high molecular weight ethylene copolymer, wherein, low-molecular ethylene polymers content is 40 ~ 50wt%, and the content of high molecular weight ethylene copolymer is 60 ~ 50wt%.
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| CN105623059B (en) * | 2014-10-27 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of polyethylene composition and its film |
| BR102015027108B1 (en) | 2014-10-27 | 2021-01-12 | China Petroleum & Chemical Corporation | polyethylene composition and film |
| CN105623057B (en) * | 2014-10-27 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of polyethylene composition and its film |
| CN105623060B (en) * | 2014-10-27 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of polyethylene composition and its film |
| CN105623056B (en) * | 2014-10-27 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of polyethylene composition and its film |
| CN105524339B (en) * | 2014-10-27 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of polyethylene film |
| EP3749707A1 (en) | 2018-02-05 | 2020-12-16 | ExxonMobil Chemical Patents Inc. | Enhanced processability of lldpe by addition of ultra-high molecular weight high density polyethylene |
| CN111057172A (en) * | 2018-10-17 | 2020-04-24 | 中国石油天然气股份有限公司 | Octene modified linear low density polyethylene resin, multilayer co-extrusion packaging film containing the same and preparation method thereof |
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| CN1662570A (en) * | 2002-06-24 | 2005-08-31 | 博里利斯技术公司 | Process for the production of a linear low-density polyethylene composition |
| CN1721451A (en) * | 2004-07-13 | 2006-01-18 | 中国石化北京燕化石油化工股份有限公司 | Process for preparing olefin copolymer with low content oligomer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1662570A (en) * | 2002-06-24 | 2005-08-31 | 博里利斯技术公司 | Process for the production of a linear low-density polyethylene composition |
| CN1721451A (en) * | 2004-07-13 | 2006-01-18 | 中国石化北京燕化石油化工股份有限公司 | Process for preparing olefin copolymer with low content oligomer |
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