CN101735348A - Double series reactor process for preparing polyethylene - Google Patents
Double series reactor process for preparing polyethylene Download PDFInfo
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- CN101735348A CN101735348A CN200910156643A CN200910156643A CN101735348A CN 101735348 A CN101735348 A CN 101735348A CN 200910156643 A CN200910156643 A CN 200910156643A CN 200910156643 A CN200910156643 A CN 200910156643A CN 101735348 A CN101735348 A CN 101735348A
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Abstract
The invention discloses a double series reactor process for preparing polyethylene, which comprises the following steps: ethylene and alpha-alkene comonomer react in a first reactor under the effect of a composite catalyst, the material in the first reactor after reaction is directly transferred to a second reactor, and ethylene and hydrogen react in the second reactor. The composite catalyst comprises: (1) a Ziegler Natta catalyst loaded on a carrier; (2) a polymer layer covered on the Ziegler Natta catalyst loaded on the carrier; and (3) a metallocene catalyst loaded in or loaded on the polymer layer. High molecular weight low-density polyethylene is produced in the first reactor, and low-molecular weight high-density resin is produced in the second reactor. No degasser is additionally arranged in the series polymerization process. The obtained polyethylene blend product has a melt flow ratio of about 40-500 and full density polyethylene of 0.900-0.975g/cm3.
Description
Technical field
The present invention relates to a kind of poly double series reactor process that is used to prepare, especially be applicable to the polyethylene that preparation has wide melt flow ratio.
Background technology
Polyethylene is a kind of very important synthetic plastics.Along with the continuous appearance of new technology and product innovation, market requires increasing to polyethylene, and for example the requirement of toughness, intensity and resisting environmental stress and cracking is more and more higher to poly use properties simultaneously.The existing high molecular of bimodal polyethylene partly provides physical strength, has low molecular weight part to improve processing characteristics again, enjoys people's favor.In addition, improve the performance of polythene material, optimize the production process of polythene material, continually develop more high-grade novel polyethylene base resin, be subject to people's attention day by day.Existing studies show that, short-chain branched distribution between the different molecular weight fraction plays crucial effects to the anti-performance of crack initiation at a slow speed and the raising polyvinyl resin grade of polythene material.Short-chain branchedly tend to be distributed in the higher level timesharing of molecular weight more, can increase the content of tie molecule in the material greatly, improved the long-term mechanical property of bimodal polyethylene tube material.
The main method of producing bimodal polyethylene at present is melt blending method, single reactor method and tandem reactor method.Wherein melt blending method is to produce the bigger and lower polymkeric substance of molecular weight, proportionally melt blending then in the reactor of parallel connection respectively.This method comprises mechanical mixing and solution mixing method, and the former is difficult to obtain enough homogeneous polymer products, thereby its quality product is difficult to guarantee.The latter then can not get widespread use owing to unit exception is expensive.
Single reactor method has that facility investment is low, and technological operation is simple, and the start-stop car is convenient, and advantage such as high lower molecular weight ratio of mixture is more even.Adopt at present single reactor to produce bimodal polyethylene mainly by composite catalyst or have the Phillips catalyzer at various active center.Yet, the polyethylene that existing P hillips catalyzer prepares in single reactor, low-molecular-weight segment is tended in its short-chain branched distribution, is unfavorable for improving the long-term mechanical property of polythene material.In addition, because the reaction parameter variation is limited in the single reactor, density of pe of producing and melt flow ratio all have certain restriction.When adopting the composite catalyst of single carrier to prepare bimodal polyethylene, the process control degree of flexibility is not high, is difficult to determine corrective measure.Because every kind of measure all can produce different influences to two kinds of different catalysts components.In addition, two kinds of different catalyzer, the promotor system may be interfering with each other.For example, organoaluminum component or the chrome catalysts that is generally used for metallocene may make metalloscene catalyst " poisoning ".(US4701432)
The cascade reaction method is the at present industrial method of producing the high-performance polyethylene material that is mainly used in.Many advanced persons' ethene polymerization process all is to adopt two still series connection or many stills to be connected on the polyvinyl resin of producing bimodal or broad peak under different reaction conditionss or the gas composition.In the series reactor process that US0052552 points out to exist at present, there is the problem of flushing.Wherein, if when first reactor is produced low molecular weight polyethylene, hydrogen a large amount of in first reactor will be brought in second reactor, make enough height of its molecular weight of High molecular weight polyethylene that second reactor produces; When if first reactor is produced High molecular weight polyethylene, owing to there is the comonomer of higher concentration in first reactor, can diffuse in second reactor, make low molecular weight polyethylene have the part side chain, influence the mechanical property of the finished product.Introduce the flash distillation dehydrogenation in this patent of EP891990, EP591990 and removed the method for comonomer.But the technology of flash distillation has increased the technology cost again greatly.
Patent CN99808337 has announced a kind of method for preparing homogeneous polyethylene material.Adopt at least one endless tube polymerization procedure and at least one gas phase polymerization step and realize.Adopt in the patent with magnesium and titanium unsupported catalysts as active ingredient, operating in the hydrogen of different quantities and comonomer carries out under existing, the highdensity relatively polymkeric substance of production lower molecular weight in the anti-device step of first what slurry endless tube uses comonomer to prepare high molecular, low-density relatively multipolymer then in Gas-phase reactor.In annular-pipe reactor, produce the melt flow rate MFR of resin
2Be at least 250g/10min, resin is at MFR in the Gas-phase reactor
50.7g/10min molecular weight is enough not high.Lower-molecular-weight component contains the comonomer less than 1wt% approximately.High molecular partly be subjected to catalyzer own limit its copolymerized ability and high molecular numerical value all is restricted.
Patent CN99808404 points out: in bimodal polyethylene is produced, especially under the situation of the first polymerization stage production low molecular weight fraction, the formation (less than the polymer particle of 150um) that typical problem is a subparticle, if there is subparticle in a large number, then can reduce the flowability of powder.This can be such as causing problem in powder transportation and the Gas-phase reactor in some processing steps.Usually in the sample of first polymerization stage (annular reactor) flash tank afterwards, find fine polymkeric substance.And the content of fine polymkeric substance depends on the MFR and the density of institute's production fraction in the annular reactor very much.The content of subparticle is subjected to used condition effect in prepolymerization reaction and the pre-polymerization reactor to a certain extent.The MFR of the polymkeric substance of in annular reactor, producing
2During increase, the content of fine polymkeric substance also increases, and what problem became in the production of bimodal polyethylene is obvious.The generation of fine polymkeric substance is too short or catalyst strength is not enough mainly due to the catalyzer residence time.Thereby the electrostatic potential that this subparticle can influence in the fluidized-bed produces knot sheet so that caking, causes device fluctuation of service so that device to stop.
Patent CN99811162 discloses the method that adopts pressure solution liquid polymeric method in the double-reactor to prepare bimodal polyethylene.Wherein first reactor usefulness has the Preparation of Catalyst High molecular weight polyethylene of phosphinimine ligand, and second reactor prepares low molecular weight polyethylene with ziegler natta catalyst.When polymerization began, raw material behind first reactor reaction, was delivered to second reactor with gained solution earlier.Can produce density 0.92g/cm
3Polyethylene.Yet this preparation method greatly reduces the homogeneity of product owing to the independent reaction of every kind of catalyzer.
Described in the patent WO9212182, it is limited to prepare its molecular weight broadening amplitude of bimodal polyethylene by composite catalyst.When adopting double-reactor to prepare, when being used to produce low molecular weight polyethylene as if first reactor, then a large amount of hydrogen and the responseless gas that exists therein need be deviate from when entering second reactor.And if when adopting traditional Z-N catalyzer first reactor to be used to produce High molecular weight polyethylene, its activity can reduce when first section polymerization in first reactor, when active ingredient enters into second-stage reaction, owing to there be the active relatively low of more hydrogen and active ingredient itself, making that its rate of polymerization is initial higherly then reduces gradually, and this just makes the residence time of second stage reactor be much higher than first stage reactor.Mean that second-stage reaction needs bigger size, and whole polymerization process is difficult to regulation and control.
Summary of the invention
The invention provides a kind of poly double series reactor process that is used to prepare, do not add any degassing facility or equipment between two tandem reactors, realized the advantage that technology is oversimplified, overcome the complicated technology of traditional tandem reactor.
A kind ofly be used to prepare poly double series reactor process, the mixture of ethene or ethene and alpha-olefin comonomer prepares the high molecular new LDPE (film grade) at the first reactor internal reaction under the effect of composite catalyst, material behind the first reactor internal reaction directly is sent to second reactor, and ethene and hydrogen prepare the lower molecular weight high density polyethylene(HDPE) at second reactor reaction;
The mol ratio of required alpha-olefin comonomer and ethene is 0-0.1 in first reactor; The mol ratio of required hydrogen and ethene is 0.01-1.0 in second reactor.
Described composite catalyst comprises:
(1) be carried on the Ziegler-Natta catalyst of carrier,
(2) cover on the ziegler natta catalyst that is carried on carrier polymer layer and
(3) be carried in the polymer layer or on metallocene catalyst.
The Ziegler-Natta catalyst that relates among the present invention, metallocene catalyst all can adopt conventional commercial catalyst, but also equal content described in the referenced patent WO2008116396 of Ziegler-Natta catalyst, polymer layer, metallocene catalyst and overlay film catalyst preparation process thereof.
A kind of preferred composite catalyst comprises:
(1) be carried on the Ziegler-Natta catalyst of carrier,
(2) cover on the ziegler natta catalyst that is carried on carrier polymer layer and
(3) be carried in the polymer layer or on metallocene catalyst and methylaluminoxane (MAO), modified methylaluminoxane (MMAO) at least a mixture among both.
When the metallocene catalyst that pre-Lip river is closed was carried on the carried catalyst surface that is covered with polymeric film, in the weight of metal in the metallocene catalyst, according to about 0.1-5wt% of polymeric film material weight, preferably about 1-3wt% took by weighing metallocene catalyst.The metallocene catalyst that takes by weighing is dissolved in forms metallocene solution, the preferred normal hexane of thinner in the thinner of nonpolar or low-pole.Select methylaluminoxane (MAO) and/or modified methylaluminoxane (MMAO) activator for use as metallocene catalyst.According to the about 1-2000 mol ratio of the metal in required aluminium and the metallocene catalyst, preferred 50-500 adds in the metallocene solution.At 0-100 ℃, preferred 60-80 ℃ of following pre-complexing 0.1-4h, preferred 0.5-2h.The carried catalyst of overlay film is dissolved in the anti-solvent of polymeric film material and forms mixture, anti-solvent be meant can not the dissolve polymer mould material solvent, the used preferred toluene of anti-solvent, iso-pentane, Skellysolve A, normal hexane or normal heptane when adopting the polymeric film material among the patent WO2008116396.The metallocene solution of above-mentioned pre-complexing is added to rapidly in the mixture, load time 0.01-4h, preferred 0.1-0.2h make metallocene be carried on polymer layer, and catalyst inner layer is gone in indiffusion as far as possible.Load temperature is about 30-90 ℃, preferred 40-80 ℃.After load finishes, remove liquid, obtain the free-pouring composite catalyst of exsiccant.
In composite catalyst of the present invention,, solved that segregate two kinds of catalyzer interact and the variety of issue that causes by isolate metallocene and metallocene catalyst with polymer layer.
First reactor and second reactor adopt the general reactor types in this area, as what slurry tank reactor, what slurry annular-pipe reactor, gas-phase fluidized-bed reactor, gas phase agitated bed reactor, preferred gas-phase fluidized-bed reactor;
Need not add any de-gassing vessel or facility between first reactor and second reactor, only linking to each other with pipeline between first reactor and second reactor gets final product.
In first reactor, the operating parameters of reactor all can adopt routine data, and space-time yield is generally at 30-200Kg/m
3* h, preferred 100Kg/m
3* h; Working pressure is at 1.0-3.0Mpa, preferred 2.5Mpa; Service temperature is at 60-130 ℃, preferred 60-100 ℃; Ethylene concentration was at 10-60% (v/v) during reaction mass was formed, preferred 30-50% (v/v); The concentration of reaction mass alpha-olefin comonomer is at 0-10% (v/v), preferred 0.1-5% (v/v), all the other are the equilibrium composition of the inert hydrocarbon of non-reaction mass component nitrogen and C1-C16, wherein preferred hydrocarbon polymer is Skellysolve A, iso-pentane, pentamethylene, hexane, heptane etc., preferred iso-pentane, hexane, concentration is at 3-20% (v/v), preferred 5-10% (v/v); Inert hydrocarbon is that new what replenish also can be to reclaim in another technological process to separate the hydrocarbon polymer that does not contain reactant.Alpha-olefin comonomer promptly adopts polyethylene reaction material commonly used, and the example of suitable alpha-olefin comonomer comprises C
1-C
20Alpha-olefin, such as but not limited to: propylene, butene-1, amylene-1, hexene-1, octene-1 or more high-grade alpha-olefin, preferably butene-1, hexene-1 and octene-1.Can in this reactor, add a certain amount of aluminum alkyls pickling agent before the polymerization.The loading level of resin calculates divided by productivity in the mean residence time available reactor of fluoropolymer resin, and the residence time of demand preferred 2 hours, was sent to the material in first reactor in second reactor at 0.5-4 hour.
In second reactor, the operating parameters of reactor all can adopt routine data, and space-time yield is generally at 30-200Kg/m
3* h, preferred 100Kg/m
3* h; Working pressure is at 1.0-3.0Mpa, preferred 2.5Mpa; Service temperature is at 60-130 ℃, preferred 80-120 ℃; Ethylene concentration was at 10-60% (v/v) during reaction mass was formed, preferred 30-50% (v/v); The concentration of reaction mass hydrogen is at 6-50% (v/v), preferred 10-30% (v/v), and all the other are non-reaction mass component nitrogen and C
1-C
16The equilibrium composition of inert hydrocarbon, wherein preferred hydrocarbon polymer is Skellysolve A, iso-pentane, pentamethylene, hexane, heptane etc., preferred iso-pentane, hexane, concentration is at 3-20% (v/v), preferred 5-10% (v/v); Inert hydrocarbon is that new what replenish also can be to reclaim in another technological process to separate the hydrocarbon polymer that does not contain reactant.Polyreaction need add an amount of aluminum alkyls as promotor, and its consumption can be selected according to the Ziegler-Natta catalyst of composite catalyst internal layer by those skilled in the art.For example, the mol ratio of metal can be 5 in described aluminum alkyl catalyst and the metallocene catalyst: 1-300: in 1 the scope, preferably 20: 1-250: in 1 the scope, and more preferably 40: 1-200: in 1 the scope.When selecting for use preferred composite catalyst to make, can not add promotor in second reactor.The residence time of fluoropolymer resin is at 0.5-12 hour, preferred 2-8 hour.
Because in the polymerization process, add comonomer in first reactor, and second interior middle a large amount of hydrogen that add of reactor, therefore, first reactor is used to prepare the high-molecular weight new LDPE (film grade), and second reactor is used to prepare low-molecular-weight high density polyethylene(HDPE).
When selecting preferred composite catalyst for use, in first reactor, can not add the alkylaluminoxane promotor or add less in right amount, the mol ratio of the aluminium in the alkylaluminoxane of adding and the metal of metallocene compound is at about 5: 1 to 100: 1, preferred 5: 1 to 50: 1.Because alkylaluminoxane under the situation that metallocene exists, mainly as the activator of metallocene catalyst, and is unfavorable for activating ziegler natta catalyst under the mol ratio of so low alkylaluminoxane and titanium compound.Therefore in first section reaction, mainly participate in reaction by metallocene catalyst.When having the alpha-olefin comonomer of less content, can grow new LDPE (film grade).In addition, because the influence of metallocene catalyst part space structure makes the poly molecular weight of its gained from low paramount, can produce MI
21Below 50g/10min, density is at 0.9-0.968g/cm
3, optimum at 0.925-0.94g/cm
3The high molecular low-density polymer.Before reactive component enters second reactor and since first reactor in alpha-olefin comonomer content lower, and the metallocene copolymerization performance a little less than, therefore, can not deviate to reflect the alpha-olefin in the component.In second reactor, since a large amount of hydrogen and the existence of alkylaluminium cpd, metallocene catalyst active centre meeting inactivation, and ziegler natta catalyst begins the performance activity in the active ingredient, thereby produces MI
2About 2-260g/10min, density are at 0.950g/cm
3The above highdensity polyethylene of lower molecular weight.Final polyethylene product has wide molecular weight distribution, and has about 20-1000, the melt flow ratio MFR of optimum about 40-600.In addition, second section catalysts has the long transformation period (greater than 6 hours), and the products distribution of High molecular weight polyethylene and low molecular weight polyethylene is very flexible, controlled in the feasible adjustment reaction product.
Technology of the present invention is simple, has saved the degassing equipment between the conventional double-reactor, production high molecular new LDPE (film grade) in first reactor, the second reactor production lower molecular weight high-density resin.When use contains the composite catalyst of promotor, only need in first reactor, once to add catalyzer, need not to add in addition again promotor.Catalyzer decay of activity in second reactor is very slow, usually actively decays to active half when the highest at least after polymerization begins 6 hours, helps fully adjusting high low-molecular-weight production allocation.Gained polyethylene blend product has melt flow ratio, the 0.900-0.975g/cm of about 40-600
3Full density polythene.
Figure of description
Fig. 1 is a device synoptic diagram of the present invention.
Embodiment
It only is in order to demonstrate the invention that following examples are provided, rather than in order to limit the scope of the invention.
Following method is used for testing the performance of the polyvinyl resin that described embodiment produces:
ASTM D1928 is used to test the density (DE) of polyvinyl resin;
ASTM D1238 is used to test the melting index (MI of polyvinyl resin
2, under the 2.16Kg load, 190 ℃) and flow index (MI
21, under the 21.6Kg load, 190 ℃).
The preparation of composite catalyst:
A: preparation (BuCp)
2ZrCl
2-M-1 composite catalyst
The M catalyzer of the preparation method referenced patent EP688794 gained of loading type ziegler natta catalyst.Under nitrogen protection, get in the reaction flask of a band stirring of 3g M catalyzer adding.In reaction flask, add the tetrahydrofuran solution (containing 0.025g polymkeric substance/ml solution) of 30ml styrene-propene acid copolymer (in the multipolymer-COOH content 3.5mmol/g polymkeric substance), stir 30min down at 0 ℃.Press then in the iso-pentane adding reaction flask of speed of per minute 1ml 50m1.Stop to stir with after allowing the solids sedimentation, remove supernatant liquor, resistates is removed iso-pentane with nitrogen purging, till obtaining free-pouring powder then with iso-pentane washing (30ml/ time) under 70 ℃.Other gets the configuration bottle that a band stirs, and adds 30ml (BuCp)
2ZrCl
2The n-heptane solution (1.9mmol/ml) that adds 8.6ml MMAO behind the hexane solution (3.75mmol/ml) again, 60 ℃ are stirred 30min down.In the catalyzer of above-mentioned overlay film, add the 20ml normal hexane, the metallocene solution of pre-complexing is poured into wherein, behind 60 ℃ of following load 10min, dry up, obtain free-pouring powder with nitrogen.
B: preparation Cp
2ZrCl
2The composite catalyst of-M-1 catalyzer
The M catalyzer of the preparation method referenced patent EP688794 gained of loading type ziegler natta catalyst.Under nitrogen protection, get in the reaction flask of a band stirring of 3g M catalyzer adding.In reaction flask, add the tetrahydrofuran solution (containing 0.025g polymkeric substance/ml solution) of 30ml styrene-propene acid copolymer (in the multipolymer-COOH content 3.5mmol/g polymkeric substance), stir 30min down at 0 ℃.Press then in the iso-pentane adding reaction flask of speed of per minute 1ml 50ml.Stop to stir with after allowing the solids sedimentation, remove supernatant liquor, resistates is removed iso-pentane with nitrogen purging, till obtaining free-pouring powder then with iso-pentane washing (30ml/ time) under 70 ℃.Other gets the configuration bottle that a band stirs, and adds 30ml Cp
2ZrCl
2The n-heptane solution (1.9mmol/ml) that adds 8.6ml MMAO behind the toluene solution (3.75mmol/ml) again, 60 ℃ are stirred 30min down.In the catalyzer of above-mentioned overlay film, add 10ml toluene, the metallocene solution of pre-complexing is poured into wherein, behind 60 ℃ of following load 10min, dry up, obtain free-pouring powder with nitrogen.
C: preparation Cp
2TiCl
2The composite catalyst of-M-1 catalyzer
The M catalyzer of the preparation method referenced patent EP688794 gained of loading type ziegler natta catalyst.Under nitrogen protection, get in the reaction flask of a band stirring of 3g M catalyzer adding.In reaction flask, add in the 30ml styrene-propene acid copolymer multipolymer-COOH content 3.5mmol/g polymkeric substance) tetrahydrofuran solution (containing 0.025g polymkeric substance/ml solution), stir 30min down at 0 ℃.Press then in the iso-pentane adding reaction flask of speed of per minute 1ml 50ml.Stop to stir with after allowing the solids sedimentation, remove supernatant liquor, resistates is removed iso-pentane with nitrogen purging, till obtaining free-pouring powder then with iso-pentane washing (30ml/ time) under 70 ℃.Other gets the configuration bottle that a band stirs, and adds 30ml Cp
2TiCl
2The n-heptane solution (1.9mmol/ml) that adds 8.6ml MMAO behind the toluene solution (3.75mmol/ml) again, 60 ℃ are stirred 30min down.In the catalyzer of above-mentioned overlay film, add 10ml toluene, the metallocene solution of pre-complexing is poured into wherein, behind 60 ℃ of following load 10min, dry up, obtain free-pouring powder with nitrogen.
Embodiment 1-6:
Adopt double-reactor device as shown in Figure 1,
R1 is first reactor;
R2 is second reactor;
L
1Be the first reactor reaction material ethene, comonomer feed line;
L
2Be that the first reactor reaction material goes out stockline, this discharging directly is added in second reactor;
L
3Be that second reactor goes out stockline;
L
4Be that the second reactor reaction material ethene, hydrogen advance feeding line.
With the adiabatic fluidized-bed polymerization reactor displacement several of nitrogen, with the ethylene gas in the full scale plant reactor is kept flowing more than the displacement 2h again to Φ 76 * 700mm.In reactor, add fresh ethylene gas 2.1Mpa, butene-1 dividing potential drop 3.8Mpa, initial reaction temperature is 60 ℃, gets above-mentioned catalyzer 0.1g, (3.0Mpa) carries into first reactor with high pressure nitrogen.Stop ethylene feed behind the 2h.Reactive component is reached in second section gas-phase fluidized-bed reactor, and with the circulating reaction gas in the full scale plant (promotor that contains suitable Z-N catalyzer), 80 ℃ participate in reaction down.Behind the reaction 4h, stop charging.Use the nitrogen replacement reactor, and reduce to envrionment temperature.Open reactor and take out polymkeric substance, weigh, the polymerization result and the product property of first reactor and second reactor are listed in table 1, and the performance of the polyethylene blend product that finally obtains is listed in table 2.
Table 1
Table 2
| Embodiment | ??MI 2??(g/10min) | ??MI 21(g/10min) | ??MFR 21/21 | Density g/cm 3 |
| ??1 | ??0.199 | ??8.3 | ??40.9 | ??0.975 |
| ??2 | ??0.12 | ??25.12 | ??209 | ??0.943 |
| ??3 | ??0.256 | ??125.8 | ??491 | ??0.900 |
| ??4 | ??3.67 | ??150.3 | ??40.9 | ??0.924 |
| Embodiment | ??MI 2??(g/10min) | ??MI 21(g/10min) | ??MFR 21/21 | Density g/cm 3 |
| ??5 | ??0.253 | ??30.16 | ??119.7 | ??0.937 |
| ??6 | ??0.081 | ??23.12 | ??285 | ??0.940 |
Claims (9)
1. one kind is used to prepare poly double series reactor process, utilize double series reactor to prepare polyethylene, it is characterized in that: the mixture of ethene or ethene and alpha-olefin comonomer at the first reactor internal reaction, obtains the high molecular new LDPE (film grade) under the effect of composite catalyst; Material behind the first reactor internal reaction directly is sent to second reactor reaction, and ethene and hydrogen obtain the lower molecular weight high density polyethylene(HDPE) at second reactor reaction;
Described composite catalyst comprises:
(1) is carried on the ziegler natta catalyst of carrier;
(2) cover polymer layer on the Ziegler-Natta catalyst that is carried on carrier; With
(3) be carried in the polymer layer or on metallocene catalyst.
2. as claimed in claim 1ly be used to prepare poly double series reactor process, it is characterized in that: described composite catalyst comprises:
(1) be carried on the ziegler natta catalyst of carrier,
(2) cover on the ziegler natta catalyst that is carried on carrier polymer layer and
(3) be carried in the polymer layer or on metallocene catalyst and at least a mixture in the methylaluminoxane, modified methylaluminoxane.
3. as claimed in claim 2ly be used to prepare poly double series reactor process, it is characterized in that: at least a mixture in metallocene catalyst and methylaluminoxane, the modified methylaluminoxane be carried in the polymer layer or on process be: in the weight of metal in the metallocene catalyst, 0.1-5% according to polymer layer weight takes by weighing metallocene catalyst, the metallocene catalyst that takes by weighing is dissolved in form metallocene solution in the thinner; For 1-2000 methylaluminoxane and/or modified methylaluminoxane are added pre-complexing in the metallocene solution according to the ratio of the metal molar in aluminium and the metallocene catalyst; The ziegler natta catalyst that is carried on carrier of overlie polymer layer is dissolved in the anti-solvent of polymer layer and forms mixture, the metallocene solution that above-mentioned pre-complexing is good is added in the mixture load time 0.01-4h; After load finishes, remove liquid, obtain the free-pouring composite catalyst of exsiccant.
4. as claimed in claim 3ly be used to prepare poly double series reactor process, it is characterized in that: the 1-3% according to polymer layer weight takes by weighing metallocene catalyst.
5. as claimed in claim 3ly be used to prepare poly double series reactor process, it is characterized in that: load time 0.1-0.2h.
6. as claimed in claim 1ly be used to prepare poly double series reactor process, it is characterized in that: described high molecular new LDPE (film grade) MI
21Below 50g/10min, density is 0.9-0.968g/cm
3
7. as claimed in claim 1ly be used to prepare poly double series reactor process, it is characterized in that: described lower molecular weight high density polyethylene(HDPE) MI
2Be 2-260g/10min, density is 0.950g/cm
3More than.
8. as claimed in claim 1ly be used to prepare poly double series reactor process, it is characterized in that: the mol ratio of required alpha-olefin comonomer and ethene is 0-0.1 in first reactor.
9. as claimed in claim 1ly be used to prepare poly double series reactor process, it is characterized in that: the mol ratio of required hydrogen and ethene is 0.01-1.0 in second reactor.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103998474A (en) * | 2011-12-28 | 2014-08-20 | 英尼奥斯欧洲股份公司 | Polymerisation process |
| CN110066365A (en) * | 2018-01-22 | 2019-07-30 | 中国石油化工股份有限公司 | A kind of preparation method of functionalized polyethy-lene |
| CN110343206A (en) * | 2018-04-03 | 2019-10-18 | 中国石油化工股份有限公司 | A kind of concatenated ethene polymerization process method of double-reactor |
| CN112313252A (en) * | 2018-05-31 | 2021-02-02 | Sabic环球技术有限责任公司 | Process for preparing multimodal polyolefins |
-
2009
- 2009-12-30 CN CN200910156643A patent/CN101735348A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103998474A (en) * | 2011-12-28 | 2014-08-20 | 英尼奥斯欧洲股份公司 | Polymerisation process |
| CN110066365A (en) * | 2018-01-22 | 2019-07-30 | 中国石油化工股份有限公司 | A kind of preparation method of functionalized polyethy-lene |
| CN110066365B (en) * | 2018-01-22 | 2021-11-16 | 中国石油化工股份有限公司 | Preparation method of functionalized polyethylene |
| CN110343206A (en) * | 2018-04-03 | 2019-10-18 | 中国石油化工股份有限公司 | A kind of concatenated ethene polymerization process method of double-reactor |
| CN112313252A (en) * | 2018-05-31 | 2021-02-02 | Sabic环球技术有限责任公司 | Process for preparing multimodal polyolefins |
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Application publication date: 20100616 |