CN1140554C

CN1140554C - Process for preparing propylene copolymers

Info

Publication number: CN1140554C
Application number: CNB988082896A
Authority: CN
Inventors: A・哈林; A·哈林; �履; P·胡温南; 顾; K·阿拉斯塔洛; �裟; J·基维莱; E·科尔霍南
Original assignee: Borealis AS
Current assignee: Borealis Technology Oy
Priority date: 1997-06-24
Filing date: 1998-06-24
Publication date: 2004-03-03
Anticipated expiration: 2018-06-24
Also published as: JP5072637B2; JP2008121028A; CN1267311A; WO1998058976A1; AU7921198A; JP2002504954A

Abstract

Described herein is a process for preparing propylene copolymers. The process comprises the steps of polymerizing propylene with comonomers in at least one slurry reactor and at least one gas phase reactor, at least 10 % of the polymer product being produced in the gas phase reactor(s); recovering from the slurry reactor a copolymerization product containing unreacted monomers and conducting the copolymerization product to a first gas phase reactor essentially without recycling of the unreacted monomers to the slurry reactor before the gas phase reactor. The process will provide high randomness copolymers, which are very soft, and copolymers having improved impact resistance.

Description

The method for preparing propene polymer

Background of invention

Invention field

The preparation that the present invention relates to the propenyl homopolymer and have the multipolymer of high comonomer content and changed anti-propene polymer towards property.Specifically, the present invention relates in the reactor assembly of a combination that comprises at least one slurry-phase reactor and at least one Gas-phase reactor, prepare the method for propene polymer.

Description of related art

The softness of propenyl polymer, shock-resistance and heat seal performance can be by improving propylene and other alkene such as copolymerization such as ethene, iso-butylenes.Substance law and gas phase process have all obtained use.But used comonomer has caused polymkeric substance swelling in the polymerisation medium of bulk process in polymerization.The result when swelling and softish polymer beads after polymerization during flash distillation, the destroyed and tap density powdered polymkeric substance of the form of particulate matter becomes very low.Simultaneously, amorphous substance gathers at powder surface.Glue, materials of low density easily gathers and produces the problem in the conveying on the flash distillation tank skin.These problems increase with the rising of comonomer ratio.

For this reason, this in the prior art polymerization is mainly by using gas phase process to carry out.Therefore, these methods are suggested and are used for preparation gluing but flowable products (EP 0237003) and rubber-like product such as EPR and EPDM (EP 0614917).In described method, the gas velocity of fluidized-bed reactor is enough to make particulate separation and its behavior to be similar to fluid.But the polymkeric substance in the fluidized-bed reactor is gone up substantially in the mode of plug flow and is passed through.

Gas phase process also is applicable to high comonomer content product, referring to EP 0674991, EP0584574, EP 0605001 and EP 0704464.

But a problem relevant with Gas-phase reactor produced by its long residence time, and its long residence time means long fringe time and possible production loss.Handle for multiple reactor, situation is all the more so.The productivity of catalyzer is low in gas phase process, this means higher catalyst costs and productive expense.

From its different advantage of drawing of slurry bulk reaction device and Gas-phase reactor, this area has the people to propose some to be used to prepare the bulk reaction device of propylene copolymer and the combination of Gas-phase reactor for respectively.But, so far, the handiness that the production that does not have a kind of art methods to satisfy to use same technical process to carry out various polyolefine grades is determined and the requirement of low productive expense.Specifically, relatively large unreacted monomer be recycled to (and this is a characteristic feature of currently known methods) in the slurry-phase reactor weakened loop reactor dynamically and slowed down to the transformation of product innovation grade.

United States Patent (USP) 4740550 discloses a kind of dual stage process that is used in the improvement of the combination propylene polymerization of loop reactor and Gas-phase reactor.The major objective of US4740550 provides the method for preparing the high quality segmented copolymer that a kind of homopolymer that distributes by the residence time that tool is narrow is delivered to the block copolymerization stage.Disclosed method comprises following phases: remove and the last shock-resistant copolymerization in another Gas-phase reactor at the material end in a body loop reactor in the fs of homopolymerization, subordinate phase homopolymerization in a Gas-phase reactor, the cyclonic separator between fs and subordinate phase.

Before the polymerisate of loop reactor was sent to gas phase, its material end part was removed and loops back loop reactor.A part is recycled directly in the fs loop reactor with described material end from the monomer of Gas-phase reactor.

The prior art exists some serious problem.Therefore, if all material ends are removed and looped back loop reactor from the reactor outlet of loop reactor, just exist loop reactor finally by the catalyzer of inactivation or the very big danger that is full of of polymeric waste material end a little.On the other hand, if a part of material later and decadent stage of a school of thought is mixed with product from a back reactor, will cause the non-uniformity problem of final product.Also have, if as US4740550 also propose with a part expect later and decadent stage of a school of thought separate collection and with an independent homopolymer blend, will cause operational complexity and heavy burden economically.

The present invention's general introduction

A target of the present invention is to eliminate the problems of the prior art of single reactor and multiple reactor processing and a kind of novel method for preparing alfon and multipolymer is provided.

Another target of the present invention provides a kind of method of highly versatile of different propylene (being total to) polymkeric substance that can be used for preparing wide region.

These targets and other target reach by the present invention hereinafter described and that propose claim together with its advantage that is better than currently known methods, and the explanation people by following patent specification can be well understood to this point.

Be based on the combination (having formed cascade like this) of at least one slurry-phase reactor of being connected in series and at least one Gas-phase reactor according to method of the present invention.Propylene (being total to) polymkeric substance prepares under the temperature and pressure that raises in the presence of a kind of catalyzer.According to the present invention, the polymerisate that contains unreacted monomer of at least one slurry-phase reactor is sent in first Gas-phase reactor, and is wherein few or do not have monomer to loop back in the slurry-phase reactor.With regard to the present invention, have been found that high-quality impact-resistant copolymer can with the homopolymerization of two stages then a shock-resistant copolymerization step prepare, wherein first or the subordinate phase copolymerization after all remove and circulation step without any the material end.In the present invention, according to purpose of the present invention by using the ordering of concrete reactor and reducing internal circulating load as far as possible by the associated throughput of selecting each reactor.

According to another aspect of the present invention, at least one slurry-phase reactor that is connected in series and at least one Gas-phase reactor are used as reactor assembly, described at least one slurry-phase reactor is the body loop reactor of operating under high temperature or supercritical temperature, and comprises that the content of the copolymerization product and the described slurry-phase reactor of the reaction medium that contains unreacted monomer uses the pipeline of interconnection slurry-phase reactor and Gas-phase reactor directly to import in the Gas-phase reactor fluidized-bed.

More precisely, mainly be to be feature according to method of the present invention with content described in the characteristic of claim 1.

The present invention has numerous important advantages.Arrange with regard to it, have been found that the monomer that is sent to first reactor can consume to a great extent or all in the Gas-phase reactor of slurry-phase reactor back.This may be the reason owing to the gas phase operation aspect of discharging a small amount of gas with polymerisate.Dynamically providing of loop reactor changes and high productivity fast in cascade.Also can start fast, because gas phase bed material can be directly from loop reactor.Can produce multiple different wide molecular weight distribution or bifurcation product with loop reactor and Gas-phase reactor cascade.Because adjustable bed level and speed of reaction, its at least one Gas-phase reactor provide the height suitability aspect the speed of reaction ratio between first and second parts of product.In addition, there is not the Gas-phase reactor of solubility limits to make it can prepare the polymkeric substance of high and very high comonomer content.

Compare with gas phase-gas phase multiple reactor processing, described loop-Gas-phase reactor combination has greatly reduced the residence time and production loss.

Brief description of drawings

Fig. 1 is the process flow diagram of first embodiment preferred of the present invention; With

Fig. 2 is the process flow diagram of second embodiment preferred of the present invention.

Detailed description of the present invention

Definition

For the purposes of the present disclosure, " slurry-phase reactor " is meant any reactor of operating and form the granular form polymkeric substance in body or slurry, such as continuous or simple stirred-tank reactor or loop reactor." body " is meant polymerization in comprising the monomeric reaction medium of at least 60% (weight).According to an embodiment preferred, slurry-phase reactor comprises a body loop reactor.

" Gas-phase reactor " is meant any mechanically mixing reactor or fluidized-bed reactor.Preferred described Gas-phase reactor comprises a mechanical stirring fluidized-bed reactor with gas velocity of at least 0.2 meter per second.

" high temperature polymerization " expression is higher than known polymerization temperature to the deleterious 80 ℃ limiting temperature of the high yield catalyzer of corresponding prior art.At high temperature, the form of the upright structure stereoregularity of catalyzer and polymer powder can be impaired.The catalyzer of the special preferred type that the present invention described below is used can't this thing happens.Described high temperature polymerization more than the limiting temperature and the temperature below the corresponding critical temperature of reaction medium carry out.

" supercritical polymerization " is meant the polymerization of carrying out under corresponding critical temperature that is higher than reaction medium and pressure.

" directly charging " is meant that the content of the slurry-phase reactor that comprises polymerisate and reaction medium directly imports to the method in the fluidized-bed of Gas-phase reactor.

" reaction zone " is meant and is used to prepare a reactor of same type or same characteristic features polymkeric substance or the reactor of several similar types that are connected in series.

Phrase " do not have substantially monomer circulation " and " few or do not have monomer to circulate " have identical meaning, be used in reference to be lower than about 30% (weight), preferably be lower than 20% (weight), particularly do not have monomer to be circulated back in the slurry treatment.On the contrary, in normal slurry process, 50% (weight) or above monomer are recycled.

Group method

The present invention relates to a kind of multi-stage method, the gas-phase reaction district of at least one Gas-phase reactor of cascade after it comprises the bulk reaction district that contains at least one slurry-phase reactor and is contained at least one slurry-phase reactor, few or do not have monomer to be circulated back to first reactor and directly or indirectly be fed to homopolymerization or the copolymerization of carrying out propylene in the gas phase.

In direct feed process, the content of slurry-phase reactor is that polymerisate and reaction medium are directly imported in the fluidized-bed reactor.It can be alternate that the product of slurry-phase reactor flows out, but successive preferably.Described slurry is derived like this, does not carry out the separation of any gas or based on the separation of the grain flow of different-grain diameter.There is not particulate matter to be sent back to preceding reactor.In order only some or all reaction mediums to be entered Gas-phase reactor polymer bed front evaporator at it, can choose wantonly the pipeline between slurry-phase reactor and the Gas-phase reactor is heated.

Described being reflected in the Gas-phase reactor proceeded.All or basically all (at least about 90%) monomer of entering Gas-phase reactor from slurry-phase reactor part of having constituted the gas reactor material stock be transformed into polymkeric substance up to it.

In the double-reactor operation, the polymkeric substance that leaves the Gas-phase reactor with discharge system enters a solid/gas separation unit.Polymkeric substance is sent to next treatment step and gas and is compressed and is circulated back to Gas-phase reactor behind purification step from the bottom.General lightweight inert substance such as methane and ethane, and heavier inert substance such as propane and oligopolymer are removed in these purification steps.Described purifying can use distillation or membrane sepn to carry out.Under the distillatory situation, monomer mainly is cycled back to Gas-phase reactor with liquid form.

In the operation of three reactors, leave first polymkeric substance and enter a solid/gas separation unit with Gas-phase reactor of discharge system.Polymkeric substance is further delivered to second Gas-phase reactor from the bottom and gas is compressed and be circulated back to first Gas-phase reactor behind purification step.General lightweight inert substance such as methane and ethane, and heavier inert substance such as propane and oligopolymer are removed in these purification steps.Described purifying can use distillation or membrane sepn to carry out.Under the distillatory situation, monomer mainly is cycled back to Gas-phase reactor with liquid form.

Choose wantonly in three reactors operations, the polymkeric substance that leaves first Gas-phase reactor with discharge system directly with the gas of following, enter second Gas-phase reactor together.

In the operation of three reactors, leave second polymkeric substance and enter a solid/gas separation unit with Gas-phase reactor of discharge system.Polymkeric substance is sent to from the bottom that further treatment step and gas are compressed and part is recirculated directly back to second Gas-phase reactor, and part is circulated back to second Gas-phase reactor behind purification step.General lightweight inert substance such as methane and ethane, and heavier inert substance such as propane and oligopolymer are removed in these purification steps.Described purifying can use distillation or membrane sepn to carry out.Under the distillatory situation, an ethylene-rich stream is cycled back to second Gas-phase reactor, and one propylene-propane stream is sent to propane and oligopolymer removal step simultaneously.

Use catalyzer to obtain polymerisate.Described catalyzer can be any enough active catalyzer that has under elevated temperature.Preferred catalyst system therefor system comprises the Ziegler-Natta catalyst that has catalyst component, gives the high yield of body in the cocatalyst component, an external donor and optional.Another kind of preferred catalyst system is based on the catalyzer of metallocenes, and for example having provides the bridged ligand of highly-solid selectively structure and impregnated on the carrier with the form of labile coordination compound.

Polymerization temperature is at least 60 ℃ and be preferably at least 65 ℃.Slurry-phase reactor operates under the elevated pressure of at least 35 Bagaos to 100 crust and Gas-phase reactor is operated to the pressure of dew-point pressure at least 10 Bagaos.Perhaps any reactor in the tandem reactor can be operated being higher than under critical temperature and the pressure.

With propylene with choose any one kind of them or multiple other C ₂To C ₁₆Alkene is ethene, 1-butylene, 4-methyl-1-pentene, 3-methyl-1-butene, 1-alkene, 1-octene, 1-decene for example, and diolefine or cycloolefin such as vinyl cyclohexane or cyclopentenes carry out polymerization and copolymerization respectively in a plurality of polymerization reactors that are connected in series.Alkene as comonomer can use in any reactor.In any one reactor, all the hydrogen of difference amount can be used as molar mass regulator.

Required propylene (being total to) polymkeric substance can reclaim from the product tripping device in gas-phase reaction district.

Catalyzer

By using catalyzer to obtain polymerisate.For catalyzer, can use any upright structure that under high temperature and possible supercritical polymerization, has the propylene of high yield and useful polymer property such as degree of isotacticity and form to select catalyzer.Used preferred catalyst system comprises the Ziegler-Natta catalyst that has catalyst component, gives the high yield of body in the cocatalyst component, an optional external donor and.Another kind of preferred catalyst system is to have the bridged ligand of highly-solid selectively structure to be provided and to have the metalloscene catalyst that impregnated in the labile coordination compound on the carrier.Finally, preferred any enough active other catalyzer that provides at elevated temperatures of described catalyzer.

The example of the catalyst system that is suitable for for example is described in the Finnish patent 86866,96615 and 88047,88048 and 88049.

Finnish patent 88047 discloses and can be used for a kind of particularly preferred catalyzer of the present invention.Finnish patent application 963707 discloses another kind of preferred catalyzer.

PCT/FI 97/00191 and PCT/FI 97/00192 disclose in addition preferred catalyzer.

Prepolymerization

Described catalyzer can prepolymerization before being sent to described placed in-line first polymerization reactor.In prepolymerization, catalyst component contacts before being sent to reactor such as olefinic monomer with monomer.The example of the system that is suitable for for example is described among the Finnish patent application FI 961152.

Also can with described prepolymerization a kind of viscous substance carry out in the presence of such as olefinic wax with storage is provided and handle in stable pre-polymerized catalyst.Pre-polymerized catalyst can easily measure the catalytic amount of sending in the polymerization reactor in wax.The example of the system that is suitable for for example is described in the Finnish patent 95387.General about 1 part of catalyzer is used for maximum 4 parts of polymkeric substance.

Be used for prepolymerized monomer and can be selected from propylene, 1-butylene, 4-methyl-1-pentene, 3-methyl-1-butene, vinyl cyclohexane, cyclopentenes, 1-hexene, 1-octene and 1-decene.

Described prepolymerization can be carried out in wax in batches or carry out in a continuous pre-polymerization reactor or in a continuous plug flow pre-polymerization reactor.

Polymerization

The present invention is the basis that is combined as with at least one slurry-phase reactor that is connected in series that is called cascade and at least one Gas-phase reactor.

The equipment of polymerization procedure can comprise the polymerization reactor of any suitable type.Described slurry-phase reactor can be that any successive of operating in body or slurry or simple stirred-tank reactor or loop reactor and polymkeric substance form in reactor with the particulate matter form.Body is meant the polymerization in comprising the monomeric reaction medium of at least 60% (weight).Described Gas-phase reactor can be any mechanically mixing reactor or fluidized-bed reactor.According to the present invention, described slurry-phase reactor is preferably the body loop reactor, and described Gas-phase reactor is preferably the fluid bed-type of reactor with mechanical stirrer.

Any reactor in described processing all can be the supercritical polymerization reactor.

When allowing that monomer is circulated back to slurry-phase reactor, the turnout ratio between slurry-phase reactor and first Gas-phase reactor (production split) was generally 67: 33 to 50: 50.On the contrary, when not needing to be circulated back to slurry-phase reactor, the turnout in slurry-phase reactor is less than or equals turnout in first Gas-phase reactor.In all cases, the turnout in the slurry-phase reactor is all greater than 10%.Therefore, according to an embodiment preferred, the polymkeric substance of 10-70% (weight), preferred 20-65% (weight), particularly 40-60% (weight) prepares in the slurry reaction district and does not have monomer to be cycled back to the slurry-phase reactor district.When the polymkeric substance of 50-67% prepares, a spot of monomer can be recycled to slurry-phase reactor from the gas-phase reaction district in the slurry reaction district.

According to the present invention, described polymerization process comprises the following step at least:

-with propylene and optional other alkene polymerization or copolymerization in first slurry polymerization district or reactor,

-reclaim polymerisate and reaction medium for the first time from first reaction zone,

-polymerisate is delivered to vapour phase polymerization district or reactor for the first time directly or indirectly,

-choose wantonly other propylene and/or comonomer are delivered to second reaction zone,

-will from the excessive propene in first district and/or comonomer and propylene that other adds and/or comonomer the first time polymerisate in the presence of carry out second time polyreaction producing the polymerisate second time,

-from second reaction zone reclaim polymerisate and

-from the reaction product separation second time and recovery polypropylene.

In addition, present method also can comprise one or more following other steps

-with one or more monomer pre-polymerized catalysts,

-from the second reaction zone product divided gas flow,

-polymerisate of the forward area that reclaims is delivered to the 3rd or the 4th reaction zone or reactor,

-choose wantonly other propylene and/or comonomer are delivered to third and fourth reaction zone,

Carry out under the existence of-polymerisate that excessive propylene and/or comonomer and propylene that other adds and/or comonomer are distinguished in front third and fourth polyreaction with produce the 3rd or the 4th polymerisate and

-from the 3rd or the 4th reaction zone reclaim polymerisate and

-separate and the recovery polypropylene from the 3rd or the 4th reaction product.

In the first step of described method, propylene and optional comonomer are fed in first polymerization reactor with deactivated catalyst title complex and optional promotor and other adjuvant component.Catalyzer can prepolymerization or prepolymerization before sending into processing.As molar mass regulator, hydrogen also can be sent in the reactor with the requirement of aforementioned component by the molar mass that obtains required polymkeric substance.Do not having recycled material to send back in the embodiment of slurry-phase reactor, having only new monomer to be sent in first reactor.

Perhaps, loop back in the embodiment of slurry-phase reactor at few monomer, the charging of reactor can comprise by a recovery system from the monomer (if any) of following reactor cycles and the new monomer that adds, hydrogen, optional comonomer and catalyst component.

In all embodiments, in the presence of propylene, optional comonomer, promotor and other adjuvant component, the activatory catalyst complexes will be in slurry-phase reactor polymerization and to form with the product that is suspended in the particle form in the round-robin fluid in reactor be polymer beads.

Polymerisation medium generally comprises monomer and choose any one kind of them hydro carbons and described fluid or for liquid or be gaseous state.Under the situation of slurry-phase reactor, particularly under the situation of loop reactor, described fluid is suspension circulation continuously in slurry-phase reactor of liquid state and polymkeric substance, can prepare the suspension of polymkeric substance in hydrocarbon medium or monomer of more particles form according to this.According to embodiment preferred, polymerization for the first time or copolyreaction are carried out in the reaction medium of mainly being made up of propylene.Preferably the medium of at least 60% (weight) is a propylene.

Select the condition of slurry-phase reactor and make at least 10% (weight) of whole production amount, preferably at least 12% (weight) polymerization in first slurry-phase reactor.Its temperature range is 40 to 110 ℃, preferred 50 to 100 ℃, for homopolymer and height random copolymers more preferably 80 to 100 ℃, and for the multipolymer of high comonomer content more preferably 60 to 75 ℃.Based on the vapour pressure of reaction medium, the reaction pressure scope is 30 to 100 crust, is preferably 35 to 80 crust.

In the slurry polymerization district, can connect and use more than one reactor.In this case, the polymer suspension in inertia hydro carbons or the monomer that produces in first slurry-phase reactor is delivered in the next slurry-phase reactor of operating under than the low pressure of preceding slurry-phase reactor under not with inert component and the regular or continuous isolating situation of monomer.

By removing heat of polymerization with the cooling jacket cooling reactor.The residence time in slurry-phase reactor must be at least 10 minutes and preferred 20 to 100 minutes to obtain the polymerization of enough degree.This is necessary for obtaining at least 40 kilograms of polyacrylic polymer yield of every gram catalyzer.When described particulate matter swelling, the high solid substrate concentration for example concerning homopolymer 50% and concerning some multipolymers 35 or 40% concentration be favourable to the operation slurry-phase reactor.If the solids concentration in the loop reactor is too low, then increased the amount of delivering to the reaction medium in second reaction zone or the Gas-phase reactor.

The content of slurry-phase reactor is that polymerisate and reaction medium are directly imported in the Gas-phase reactor fluidized-bed.

Described second reactor is preferably Gas-phase reactor, wherein propylene and optional comonomer polymerization in the reaction medium of gas or steam composition.

Although can use the Gas-phase reactor of other type, described Gas-phase reactor can be the fluidized-bed reactor of a routine.In fluidized-bed reactor, described bed forms also ever-increasing polymer beads by institute and forms with the still active catalyzer of polymer moieties.Described bed by import gaseous fraction as so that as described in the particulate matter monomer that becomes flow rate of fluid (at least 0.2 meter per second) to import remain on fluidized state.Described fluidizing agent also can comprise rare gas element such as nitrogen and also as the hydrogen of conditioning agent.In the present invention, do not recommend to use the unnecessary rare gas element that may have problems in recovery part.

Used Gas-phase reactor can be operated under the reaction pressures of 50 to 115 ℃, preferred 60 to 110 ℃ temperature range and 10 to 40 crust, and monomeric dividing potential drop is preferably between 2 to 30 crust or higher, but always is lower than dew-point pressure.

According to an embodiment preferred, except various flushings required do not have new propylene to be sent in first Gas-phase reactor.

For for example gaseous state of separate part and possible the volatile constituent heavy comonomer and the compound of catalyzer raw material (for example as) in flash tank, comprise gas reaction medium the second time polymerisate pressure after first Gas-phase reactor, be lowered.Overhead gas stream loops back first Gas-phase reactor by recovery system or part is got back to first Gas-phase reactor and part is got back to slurry-phase reactor.Some monomers generally are the heavier comonomer bulk reaction districts that arrives capable of circulation.

If desired, polymerisate can be sent to second Gas-phase reactor and carry out polyreaction for the third time to produce the polymerisate that can therefrom separate and reclaim MODIFICATION OF POLYPROPYLENE.For the third time polyreaction give the comonomer of polymerisate character for the third time as shock strength, ductility or the pliability of improvement in the presence of in Gas-phase reactor, carry out.Generally, remove in the depressurization steps of gas before second Gas-phase reactor of part from first Gas-phase reactor.The gas of being removed is compressed to recovery part and by described processing under the double-reactor situation.Perhaps, product can directly be transferred to the 3rd reactor for the second time.

In general, if multipolymer is according to the inventive method preparation, they contain the comonomer of at least 0.5% (weight), the particularly comonomer at least about 2% (weight) and also preferably contain high at least a comonomer to 20% (weight) so.The general comonomer content of delivering to the multipolymer of first Gas-phase reactor is about 2-16% (weight).The multipolymer that produces can show highly random character (very softish multipolymer).

Particularly, described polymerisate can be sent to second Gas-phase reactor and provide rubbery copolymer with the polyreaction that (is total to) for the third time of the polymerisate by forming modification.This polyreaction for the third time will provide for example polymerisate character of the shock strength of improvement.Thisly provide elastomeric step to carry out in every way.Therefore, propylene becomes elastomerics to prepare with ethylene copolymer to preferred elastomerics by inciting somebody to action at least.The condition of copolymerization is in the EPM of routine working condition limit, and this EPM working condition is disclosed in 545 to 558 pages of Encyclopediaof Polymer Science and Engineering of the 6th volume of second edition for example.If the ethylene repeating unit content in the polymkeric substance within the specific limits, just formed the rubber-like product.Therefore, preferably ethene is become elastomerics with copolymerization of propylene with the ratio that finally makes multipolymer comprise 10 to 70% (weight) ethylene unit.Specifically, acetate unit content is elastomeric 30 to 50% (weight) of described multipolymer propylene/ethylene.In other words, ethene and propylene are copolymerized into elastomerics with 30/70 to 50/50 ethylene/propene molar ratio.

Described elastomerics also can be by providing in the polymerisate that prefabricated or natural elastomerics is joined first Gas-phase reactor.

Impact modified polypropylene generally comprises the above-mentioned elastomerics of about 5-50% (weight), particularly about 10-45% (weight) and preferred about 15-40% (weight).

In general, the impact property that is improved in order to reach higher molar mass, the density of hydrogen of reaction product is lowered before product is fed to second gas phase for the second time.

Also the product of second gas-phase reaction may be transferred to the 3rd (fourth class) polymerization zone, wherein copolymerization is carried out in the presence of the comonomer of the character of giving trimerization product improvement.

Described third and fourth Gas-phase reactor can be operated under 60 to 80 ℃ temperature, and reaction pressure can remain on 10 to 30 crust.

Described above summarizing, a particularly preferred embodiment according to the invention comprises (Fig. 1)

-be that 40 to 80 crust, temperature are polypropylene in 80 to 100 ℃ the loop reactor at a pressure, hydrogen is used to the molar mass of controlled polymerization product,

-reclaim polymerisate and be sent to the Gas-phase reactor fluidized-bed from loop reactor,

-optional propylene and the optional comonomer that other is added delivered to Gas-phase reactor,

-optional the hydrogen that other is added is delivered to Gas-phase reactor provides required polymerisate with control hydrogen/propylene ratio molecular mass,

-reclaim polymerisate and send it to flash tank from Gas-phase reactor, wherein the pressure of product is lowered the bottoms that contains the tank deck product of unreacting propylene and hydrogen basically and mainly comprise the polymeric solids to produce,

-by recovery part with the tank deck product or at least its major portion be recycled to Gas-phase reactor and

-recovery is as the polyacrylic polymer of flash tank bottoms.

According to second kind of particularly preferred embodiment (Fig. 1):

-be that 40 to 80 crust, temperature are that polypropylene and comonomer such as ethene or 1-butylene or both and hydrogen are used to provide the polymerisate with required molar mass in 60 to 80 ℃ the loop reactor at a pressure,

-self-loop reactor polymerisate directly is sent to the Gas-phase reactor fluidized-bed in the future,

-will choose the propylene and the comonomer that add in addition wantonly to deliver to Gas-phase reactor,

-will choose the hydrogen that adds in addition wantonly to deliver to Gas-phase reactor provides required molar mass with control hydrogen/propylene ratio polymerisate,

-reclaim polymerisate and send it to flash tank from Gas-phase reactor, wherein pressure is lowered the bottoms that contains the tank deck product of unreacted monomer and hydrogen basically and mainly comprise the polymeric solids to produce,

-recovery is as the polyacrylic polymer of flash tank bottoms.

According to the third particularly preferred embodiment (Fig. 2):

-be that 40 to 80 crust, temperature are the molar mass that polypropylene and optional comonomer and hydrogen are used to the controlled polymerization product in 60 to 100 ℃ the loop reactor at a pressure,

-will choose the propylene and the optional comonomer that add in addition wantonly to deliver to Gas-phase reactor,

-optional the hydrogen that other is added is delivered to Gas-phase reactor provides the desired molecule quality with control hydrogen/propylene ratio polymerisate,

-reclaim polymerisate and send it to the intermediate flash tank from first Gas-phase reactor, wherein the pressure of product is lowered the bottoms that contains the tank deck product of unreacted monomer and hydrogen basically and mainly comprise the polymeric solids to produce,

-by recovery part with the tank deck product or at least its major portion be recycled to first Gas-phase reactor,

-by the polymer feed system, will deliver to polyreaction for the third time from the polyacrylic polymer of intermediate flash tank bottom,

-in the presence of comonomer, in a Gas-phase reactor, carry out polyreaction for the third time,

-retrieve from the polymerisate of second Gas-phase reactor and be sent to a flash tank, wherein the pressure of product is lowered the bottoms that contains the tank deck product of unreacted monomer and hydrogen basically and mainly comprise the polymeric solids to produce,

-can choose wantonly and will directly or through a flash tank be sent to the 3rd (fourth class) gas-phase polymerization reactor from polymeric polymerisate for the third time, wherein be aggregated under the existence of comonomer and carry out.

Two kinds of above-mentioned embodiment preferred are also shown in the concrete accompanying drawing of arranging of the used treatment facility of explanation.It is numbered corresponding to following concrete equipment:

1; 101 pre-polymerization reactors

30; 130 catalyst stores devices

31; 131 feeding units

32; 132 thinners (choosing wantonly)

33; 133 catalyzer/diluent mixture

34; 134 monomers

35; 135 promotors and the body of giving that may use

40; 140 loop reactors

42; 142 diluent feed (choosing wantonly)

43; 143 monomer feed

44; 144 hydrogen feed

45; 145 comonomer chargings (choosing wantonly)

46; 146 by pipeline 46; 146 return loop reactors 40; 140

47; 147 one or several vent valves

The 150b flash separator

152b removes pipeline

60; 160; The 160b Gas-phase reactor

61; 161; The 161b gas delivery line

62; 162; The 162b compressor

63; 163; The 163b monomer feed

64; 164; The charging of 164b comonomer

65; 165; The 165b hydrogen feed

66; 166; The 166b transfer line

67; 167 product transfer lines

68; 168 polymerisate recovery system such as flash tanks

69; 169 receive pipeline

70; 170 MONOMER RECOVERY systems

With reference to Fig. 1, can notice from the catalyzer of storer 30 and deliver to feeding unit 31 with optional thinner from pipeline 32.Feeding unit 31 is sent to prepolymerization chamber 1 with catalyzer/diluent mixture through pipeline 33.Monomer is sent into by 34, promotor and may with the body of giving can be sent to reactor 1 or preferably with promotor with mix for body mutually to be incorporated in pipeline 35 and send into by pipeline 35.

Preferably directly pre-polymerized catalyst is removed and is sent to loop reactor 40 from prepolymerization chamber 1 by pipeline 36.In loop reactor 40, make polymerization continue to carry out by adding through pipeline 46 from the optional thinner of pipeline 42, from the monomer of pipeline 43, from the hydrogen of pipeline 44 with from the optional comonomer of pipeline 45.Optional promotor also can import in the loop reactor 40.

Polymkeric substance-hydrocarbon mixture is sent by one or several vent valve described in the Finnish patent application 971368 or 971,367 47 for example from loop reactor 40.A direct product transfer line 67 is arranged between loop reactor 40 and Gas-phase reactor 60.

Bottom in Gas-phase reactor 60, by a fluidized-bed of being made up of polymer beads, polymer beads remains on fluidized state by circulating to the bottom of reactor 60 through pipeline 61, compressor 62 and heat exchanger (not shown) with normal way from the gas of the top removal of reactor 60.Reactor 60 can be furnished with mixing tank (described in Finnish patent application 933073, not showing in the drawings) valuably, but this is not essential.To the bottom of reactor 60 import monomer in known manner from pipeline 63, from the optional comonomer of pipeline 64 with from the hydrogen of pipeline 65.Product can be by transfer line 66 from the reactor 60 continuous or periodic flash tanks 68 that are discharged into.The top product of recovery system through the MONOMER RECOVERY systemic circulation to Gas-phase reactor.

Embodiment shown in Figure 2 just is different from Fig. 1 on the product from Gas-phase reactor 160 is sent to the meaning of other Gas-phase reactor 160b.Polymer beads shifts out and delivers to Gas-phase reactor 160b from flash tank 168 and polymer feed jar 150b through removing pipeline 152b.Described Gas-phase reactor advantageously is furnished with the mixing tank (not shown).

The top product of flash separator 168b is partly recirculated to Gas-phase reactor 160b and is partly recirculated to the MONOMER RECOVERY system.

In two kinds of above-mentioned embodiments, numbering 70 and 170 expressions can with the recycle monomer of Gas-phase reactor (60,160 and 160b) or separator (68,168 and 168b) and hydrogen and/or generally boiling point be lower than the isolating tripping device of monomeric light inertia hydro carbons such as film unit or stripping tower.

Polymkeric substance

The product of producing according to the present invention comprises the polypropylene copolymer that contains polypropylene terpolymer.Specifically, can produce very soft high random copolymers by means of the present invention.Described multipolymer comprises at least 0.5% (weight) comonomer, particularly at least about 2% (weight) and be preferably up to the comonomer of 20% (weight).General comonomer content is about 2 to 12% (weight).An essential characteristic of the present invention is preferred used high polymerization temperature more than 75 ℃, and it can provide more uniform comonomer to distribute in copolymerization.By the degree of randomness that fourier transform infrared spectrometry records, when 60 ℃ polymerization temperature, be 69%, in the time of 65 ℃, be 71%, at the polymerization temperature of 75 ℃ of first reactors with under the polymerization temperature of 80 ℃ of second reactors, be 74%.

The other product of producing by the present invention comprises impact modified propene polymer, preferably comprises the rubbery copolymer of the shock-resistance of having improved product, particularly ethylene-propylene copolymer.Described elastomerics has the polyacrylic ratio of about 5-40% (weight).

Detail description embodiment is used to illustrate mechanism of the present invention.

Embodiment 1

Simulate the continuous preparation facility of production-scale homopolymer polypropylene.The preparation facility comprises catalyzer, alkane, gives body, propylene feed system, pre-polymerization reactor, loop reactor and gas fluidized bed reactor (GPR).

With catalyzer, alkane, send into pre-polymerization reactor for body and propylene.To be sent to loop reactor from the polymer slurries of pre-polymerization reactor, and send into hydrogen and more propylene to loop reactor simultaneously.The polymer slurries of self-loop reactor is sent to GPR with hydrogen and the propylene that other adds in the future.Be respectively in each reactor productivity: 10 tons/hour of 300 kilograms/hour of pre-polymerization reactors, 15 tons/hour of loop reactors and GPR.

The prepolymerization loop reactor is operated under the pressure of 56 crust and 20 ℃ temperature.Loop reactor is operated under the pressure of 55 crust and 85 ℃ temperature.By the control hydrogen feed, the MFR of the homopolymer polypropylene that will produce in loop reactor (2.16kg, 230 ℃) is adjusted to 1.

GPR operates under the pressure of 35 crust and 85 ℃ temperature.Dividing potential drop by control hydrogen is adjusted to 13 with the MFR (2.16kg, 230 ℃) of the homopolymer polypropylene that GPR produces.5 tons/hour propylene are looped back loop reactor from the GPR outlet.The per pass conversion of propylene is 83%.

Embodiment 2

The production-scale facility of the homopolymer polypropylene of the good impact property of simulation continuous production tool.Described facility comprises catalyzer, alkane, gives body, propylene feed system, pre-polymerization reactor, loop reactor and two gas fluidized bed reactors (referring to Fig. 2).

With catalyzer, alkane, send into pre-polymerization reactor for body and propylene.To be sent to loop reactor from the polymer slurries of pre-polymerization reactor, and send into hydrogen and more propylene to loop reactor simultaneously.The polymer slurries of self-loop reactor is sent to first GPR with hydrogen and the propylene that other adds in the future.

Before entering second GPR, will be from the polymkeric substance decompression of first GPR.Ethene and the propylene that other adds are sent to second GPR.

Be respectively in each reactor productivity: 300 kilograms/hour of pre-polymerization reactors, 15 tons/hour of loop reactors, 6 tons/hour of 10 tons/hour and second GPR of first GPR.

The prepolymerization loop reactor is operated under the pressure of 56 crust and 20 ℃ temperature.Loop reactor is operated under the pressure of 55 crust and 85 ℃ temperature.MFR (2.16kg, 230 ℃) by the homopolymer polypropylene that will produce in loop reactor of control hydrogen feed is adjusted to 20.

First GPR operates under the pressure of 35 crust and 85 ℃ temperature.Dividing potential drop by control hydrogen is adjusted to 20 with the MFR (2.16kg, 230 ℃) of the homopolymer polypropylene that first GPR produces.4.3 tons/hour propylene are looped back loop reactor from the GPR outlet.

Second GPR operates under the temperature of the pressure of 20 crust and 70 ℃.Dividing potential drop by control hydrogen is adjusted to 13 with the MFR (2.16kg, 230 ℃) of the homopolymer polypropylene that second GPR produces.2.7 tons/hour propylene are looped back loop reactor and with ethylene recycle to the second GPR of 1.6 tons/hour from second GPR outlet.

Embodiment 3

The production-scale facility of the polyacrylic polymer that the simulation continuous production is random.Described facility comprises catalyzer, alkane, gives body, propylene and ethene feeder system, pre-polymerization reactor, loop reactor and a gas fluidized bed reactor (GPR).

With catalyzer, alkane, send into pre-polymerization reactor for body and propylene.To be sent to loop reactor from the polymer slurries of pre-polymerization reactor.Send into ethene, hydrogen and more propylene to loop reactor.The polymer slurries of self-loop reactor is sent to GPR with hydrogen, ethene and the propylene that other adds in the future.Be respectively in each reactor productivity: 10 tons/hour of 300 kilograms/hour of pre-polymerization reactors, 15 tons/hour of loop reactors and GPR.

Pre-polymerization reactor is operated under the pressure of 56 crust and 20 ℃ temperature.Loop reactor is operated under the pressure of 55 crust and 75 ℃ temperature.MFR (2.16kg, 230 ℃) by the Atactic Polypropelene that will produce in loop reactor of control hydrogen feed is adjusted to 7, and by ethylene feed ethylene content is adjusted to 3.5% (weight).

GPR operates under the pressure of 35 crust and 80 ℃ temperature.Dividing potential drop by control hydrogen is adjusted to 7 with the MFR (2.16kg, 230 ℃) of the Atactic Polypropelene that GPR produces, and by the dividing potential drop of regulating ethene ethylene content is set in 3.5% (weight).The ethene of 5 tons/hour propylene and 33 kilograms/hour is looped back loop reactor from the GPR outlet.The per pass conversion of propylene and ethene is respectively 83% and 96%.

Embodiment 4

The production-scale facility of the polypropylene copolymer of simulation good impact property of continuous production tool and creeping property.Described facility comprises catalyzer, alkane, gives body, ethene and propylene feed system, pre-polymerization reactor, loop reactor, flash tank and two gas fluidized bed reactors.

With catalyzer, alkane, send into pre-polymerization reactor for body and propylene.To be sent to loop reactor from the polymer slurries of pre-polymerization reactor, and send into hydrogen and more propylene to loop reactor simultaneously.The polymer slurries of self-loop reactor is sent to propylene and the isolating flash tank of polymkeric substance in the future.

To be sent to first GPR from the polymkeric substance of flash tank.To after removing hydrogen, be sent to first GPR from the propylene of flash tank.Ethene and the propylene that other adds are sent to first GPR.To be sent to second GPR from the polymkeric substance of first GPR.Ethene, some hydrogen and the propylene that adds in addition are sent to second GPR.

Be respectively in each reactor productivity: 300 kilograms/hour of pre-polymerization reactors, 10 tons/hour of loop reactors, 6 tons/hour of 10 tons/hour and second GPR of first GPR.

Pre-polymerization reactor is operated under the pressure of 56 crust and 20 ℃ temperature.Loop reactor is operated under the pressure of 55 crust and 85 ℃ temperature.MFR (2.16kg, 230 ℃) by the homopolymer polypropylene that will produce in loop reactor of control hydrogen feed is adjusted to 100.

Described GPR operates under the pressure of 35 crust and 80 ℃ temperature.The hydrogen of the propylene by turnout ratio between the controlling reactor and flash distillation is removed efficient the polyacrylic MFR (2.16kg, 230 ℃) of described GPR is adjusted to 0.4.By the dividing potential drop and the turnout ratio between the controlling reactor of regulating ethene ethylene content is set in 2% (weight).

Second GPR operates under the temperature of the pressure of 20 crust and 70 ℃.The MFR (2.16kg, 230 ℃) of dividing potential drop by control hydrogen and the polypropylene copolymer second GPR produced by the turnout ratio between the controlling reactor is adjusted to 0.3.A spot of propylene is looped back loop reactor from second GPR.

Embodiment 5

The production-scale facility of the polypropylene copolymer of the good creeping property of simulation continuous production tool.Described facility comprises catalyzer, alkane, gives body, ethene and propylene feed system, pre-polymerization reactor, loop reactor, flash tank and gas fluidized bed reactor.

With catalyzer, alkane, send into pre-polymerization reactor for body and propylene.To be sent to loop reactor from the polymer slurries of pre-polymerization reactor, and in loop reactor, send into ethene and more propylene simultaneously.The polymer slurries of self-loop reactor is sent to monomer and the isolating flash tank of polymkeric substance in the future.

To be sent to GPR from the polymkeric substance of flash tank.To after removing ethene, be sent to GPR from the propylene of flash tank.Hydrogen and the propylene that other adds are sent to GPR.

Be respectively in each reactor productivity: 10 tons/hour of 300 kilograms/hour of pre-polymerization reactors, 10 tons/hour of loop reactors and first GPR.

Embodiment 6

Use the pilot plant of operation continuously to produce homopolymer polypropylene.Described equipment comprises catalyzer, alkane, gives body, propylene feed system, pre-polymerization reactor, loop reactor and gas fluidized bed reactor (GPR).

With catalyzer, alkane, send into pre-polymerization reactor for body and propylene.To be sent to loop reactor from the polymer slurries of pre-polymerization reactor, and send into hydrogen and more propylene to loop reactor simultaneously.The polymer slurries of self-loop reactor is sent to GPR with hydrogen and the propylene that other adds in the future.

After removing polymerisate, separate formed polymkeric substance and unreacted propylene from GPR.

Used catalyzer is high activity and the stereospecific ZN-catalyzer according to United States Patent (USP) 5234879 preparations.Before being sent to pre-polymerization reactor, with described catalyzer and triethyl aluminum (TEA) and dicyclopentyl dimethoxyl silane (DCPDMS) (the Al/Ti ratio is 250, and Al/Do is 40 (moles)) contact.

Described catalyzer is joined in the pre-polymerization reactor according to United States Patent (USP) 5385992 chargings and with the propylene flushing.Described pre-polymerization reactor is operated under the temperature of 51 bar pressures and 20 ℃, and the mean residence time of catalyzer is 7 minutes.

Pre-polymerized catalyst, propylene and other component are transferred to loop reactor.Described loop reactor is operated under the pressure of 50 crust and 80 ℃ temperature, and the mean residence time of catalyzer is 1 hour.By the control hydrogen feed MFR (2.16kg, 230 ℃) of the homopolymer polypropylene produced in the loop reactor is adjusted to 7.

The polymer slurries of self-loop reactor is transferred to GPR in the future.Described GPR reactor is operated under the partial pressure of propylene of 29 total pressures of clinging to and 21 crust.Temperature is that the mean residence time of 90 ℃ and catalyzer is 1 hour.The MFR (2.16kg, 230 ℃) of the homopolymer polypropylene that described GPR produces is 7 and controls by the dividing potential drop of regulating hydrogen.Turnout ratio between the reactor is: pre-polymerization reactor is 1%, loop reactor be 49% and GPR be 50%.Catalyst productivity is 32 kilograms of polypropylene of every gram catalyzer.

Embodiment 7

The polymkeric substance that forms is separated after shifting out from GPR with unreacted propylene.

Used catalyzer is high activity and the stereospecific ZN-catalyzer according to Finnish patent application 963707 preparations.Before being sent to pre-polymerization reactor, with described catalyzer and triethyl aluminum (TEA) and dicyclopentyl dimethoxyl silane (DCPDMS) (the Al/Ti ratio is 250, and Al/Do is 40 (moles)) contact.

Described catalyzer is punched in the pre-polymerization reactor according to United States Patent (USP) 5385992 chargings and with propylene.Described pre-polymerization reactor is operated under the temperature of 53 bar pressures and 20 ℃, and the mean residence time of catalyzer is 7 minutes.

Pre-polymerized catalyst, propylene and other component are transferred to loop reactor.Described loop reactor is operated under the pressure of 52 crust and 85 ℃ temperature, and the mean residence time of catalyzer is 1 hour.By the control hydrogen feed MFR (2.16kg, 230 ℃) of the homopolymer polypropylene produced in the loop reactor is adjusted to 7.

The polymer slurries of self-loop reactor is transferred to GPR in the future.Described GPR operates under the partial pressure of propylene of 29 total pressures of clinging to and 21 crust.The temperature of GPR is that the mean residence time of 80 ℃ and catalyzer is 1 hour.The MFR (2.16kg, 230 ℃) of the homopolymer polypropylene that described GPR produces is 7 and regulates by the dividing potential drop of control hydrogen.Turnout ratio between the reactor is: pre-polymerization reactor is 1%, loop reactor be 53% and GPR be 48%.Catalyst productivity is 50 kilograms of polypropylene of every gram catalyzer.

Embodiment 8

Described catalyzer is punched in the pre-polymerization reactor according to United States Patent (USP) 5385992 chargings and with propylene.Described pre-polymerization reactor is operated under the temperature of 58 bar pressures and 20 ℃, and the mean residence time of catalyzer is 7 minutes.

Pre-polymerized catalyst, propylene and other component are transferred to loop reactor.

Described loop reactor is operated under the pressure of 57 crust and 80 ℃ temperature, and the mean residence time of catalyzer is 2 hours.By the control hydrogen feed MFR (2.16kg, 230 ℃) of the homopolymer polypropylene produced in the loop reactor is adjusted to 375.

The polymer slurries of self-loop reactor is transferred to GPR in the future.Described GPR operates under the partial pressure of propylene of 29 total pressures of clinging to and 16 crust.The temperature of reactor is that the mean residence time of 80 ℃ and catalyzer is 2 hours.The MFR (2.16kg, 230 ℃) of the homopolymer polypropylene that described GPR produces is 450 and regulates by the dividing potential drop of control hydrogen with by the turnout ratio between controlling reactor.The turnout ratio is adjusted to: pre-polymerization reactor is 1%, loop reactor be 50% and GPR be 49%.

Embodiment 9

Use the pilot plant of operation continuously to produce the polypropylene unregulated polymer.Described equipment comprises catalyzer, alkane, gives body, propylene and ethene feeder system, loop reactor and gas fluidized bed reactor (GPR).

With catalyzer, alkane, send into pre-polymerization reactor for body and propylene.The polymer slurries of self-loop reactor is sent to GPR with hydrogen, propylene and the ethene that other adds in the future.The polymkeric substance that forms is separated after shifting out from GPR with unreacted propylene.

Used catalyzer is high activity and the stereospecific ZN-catalyzer according to United States Patent (USP) 5234879 preparations.Described catalyzer is according to Finnish patent 95387 usefulness propylene prepolymerizations in batches (quality ratio of polypropylene/catalyzer is 10).Before being sent to loop reactor, with described pre-polymerized catalyst and triethyl aluminum (TEA) and dicyclopentyl dimethoxyl silane (DCPDMS) (the Al/Ti ratio is 140, and Al/Do is 10 (moles)) contact.

Described catalyzer is punched in the loop reactor according to United States Patent (USP) 5385992 chargings and with propylene.Described loop reactor is operated under the temperature of 50 bar pressures and 75 ℃, and the mean residence time of catalyzer is 1 hour.By the control hydrogen feed MFR (2.16kg, 230 ℃) of the polypropylene unregulated polymer produced in the loop reactor is adjusted to 4.By the control ethylene feed ethylene content is controlled to 3.5% (weight).

The polymer slurries of self-loop reactor is transferred to GPR in the future.Described GPR reactor is operated under the partial pressure of propylene of 29 total pressures of clinging to and 21 crust.The service temperature of GPR is that the mean residence time of 80 ℃ and catalyzer is 1.5 hours.The MFR (2.16kg, 230 ℃) of the polypropylene unregulated polymer that described GPR produces is adjusted to 4 by the dividing potential drop of control hydrogen.Ethylene content is adjusted to 3.5% (weight) by the control ethylene partial pressure.Turnout ratio between the reactor is: loop reactor be 55% and GPR be 45%.

Embodiment 10

With catalyzer, alkane, send into pre-polymerization reactor for body and propylene.The polymer slurries of self-loop reactor reaches the hydrogen and the propylene that add in addition and is sent to GPR in the future.The polymkeric substance that forms is separated after shifting out from GPR with unreacted propylene.

Used catalyzer is high activity and the stereospecific ZN-catalyzer according to United States Patent (USP) 5234879 preparations.Described catalyzer is according to Finnish patent 95387 usefulness propylene prepolymerizations in batches (quality ratio of polypropylene/catalyzer is 10).Before being sent to loop reactor, with described pre-polymerized catalyst and triethyl aluminum (TEA) and dicyclopentyl dimethoxyl silane (DCPDMS) (the Al/Ti ratio is 135, and Al/Do is 10 (moles)) contact.

Described catalyzer is punched in the loop reactor according to United States Patent (USP) 5385992 chargings and with propylene.Described loop reactor is operated under the temperature of 50 bar pressures and 75 ℃, and the mean residence time of catalyzer is 1 hour.By the control hydrogen feed MFR (2.16kg, 230 ℃) of the polypropylene unregulated polymer produced in the loop reactor is adjusted to 0.2.By the control ethylene feed ethylene content is adjusted to 3.5% (weight).

The polymer slurries of self-loop reactor is transferred to GPR in the future.Described GPR reactor is operated under the partial pressure of propylene of 29 total pressures of clinging to and 21 crust.The service temperature of GPR is that the mean residence time of 80 ℃ and catalyzer is 1.5 hours.The MFR (2.16kg, 230 ℃) of the polypropylene unregulated polymer that described GPR produces is adjusted to 3 by the dividing potential drop of control hydrogen.Ethylene content is set to 1.8% (weight) by the turnout ratio between the conditioned reaction device.Required ethylene content loop reactor be 40% and GPR obtain under 60% the turnout ratio.

Described pre-polymerization reactor is operated under the pressure of 56 crust and 20 ℃ temperature.Loop reactor is operated under the pressure of 55 crust and 75 ℃ temperature.The MFR of the Atactic Polypropelene of in loop reactor, producing (2.16kg, 230 ℃) be lower than 0.1 and ethylene content by control ethylene feed be adjusted to 3.5% (weight).

Described GPR reactor is operated under the pressure of 35 crust and 80 ℃ temperature.The MFR (2.16kg, 230 ℃) of the polypropylene copolymer of described GPR being produced by the control hydrogen partial pressure is adjusted to 0.3.By the turnout ratio between the conditioned reaction device ethylene content is set in 1.8% (weight).

Reclaim the ethene of loop reactor outlet and loop back loop reactor from flash gas.The propylene of GPR outlet is reclaimed and delivers to loop reactor after removing hydrogen.The per pass conversion of propylene and ethene is respectively 83% and 84%.

Embodiment 11

Use the pilot plant of operate continuously to produce the polypropylene copolymer of good impact property of tool and creeping property.Described equipment comprises catalyzer, alkane, gives body, propylene and ethene feeder system, pre-polymerization reactor, loop reactor and two gas fluidized bed reactors (GPR).

With catalyzer, alkane, send into pre-polymerization reactor for body and propylene.To be sent to loop reactor from the polymer slurries of pre-polymerization reactor, and the propylene of sending into hydrogen, ethene and adding in addition to loop reactor simultaneously.

The polymer slurries of self-loop reactor is sent to first GPR with hydrogen and the propylene that other adds in the future.To be sent to second GPR from the polymkeric substance of first GPR.Ethene, some hydrogen and the propylene that adds in addition are sent to second GPR.The polymkeric substance that forms is separated after discharging from second GPR with unreacted propylene.

Used catalyzer is high activity and the stereospecific ZN catalyzer according to United States Patent (USP) 5234879 preparations.Before being sent to pre-polymerization reactor, with described catalyzer and triethyl aluminum (TEA) and dicyclopentyl dimethoxyl silane (DCPDMS) (the Al/Ti ratio is 150, and Al/Do is 10 (moles)) contact.

Described catalyzer is punched in the loop reactor according to United States Patent (USP) 5385992 chargings and with propylene.Described pre-polymerization reactor is operated under the temperature of 51 bar pressures and 20 ℃, and the mean residence time of catalyzer is 7 minutes.

Described loop reactor mean residence time of operation and catalyzer under the pressure of 50 crust and 75 ℃ temperature is 1 hour.By the control hydrogen feed MFR (2.16kg, 230 ℃) of the polypropylene unregulated polymer produced in the loop reactor is adjusted to 7.By the control ethylene feed ethylene content is adjusted to 3.5% (weight).

The polymer slurries of self-loop reactor is transferred to first GPR in the future.First GPR reactor is operated under the partial pressure of propylene of 29 total pressures of clinging to and 21 crust.Its service temperature is that the mean residence time of 80 ℃ and catalyzer is 1.5 hours.The MFR (2.16kg, 230 ℃) of the polypropylene unregulated polymer that described GPR produces is adjusted to 10 by the dividing potential drop of control hydrogen.Ethylene content is set to 2% (weight) by the turnout ratio between the conditioned reaction device.

To transfer to second GPR from the polymkeric substance of first GPR.Second GPR operates under the monomer dividing potential drops of 10 total pressures of clinging to and 7 crust.Its service temperature is that the mean residence time of 80 ℃ and catalyzer is 1.5 hours.The MFR (2.16kg, 230 ℃) of the polypropylene copolymer that described GPR produces is adjusted to 7 by the dividing potential drop of control hydrogen.Ethylene content is set to 10% (weight) by the dividing potential drop of adjusting ethene with by the turnout ratio between controlling reactor.

Be 1% at pre-polymerization reactor, loop reactor is 40%, first GPR is that 40% and second GPR obtains required character under 19% the turnout ratio.

Embodiment 12

Use the pilot plant of operation continuously to produce very softish polypropylene copolymer.Described equipment comprises catalyzer, alkane, gives body, propylene and ethene feeder system, pre-polymerization reactor, loop reactor and gas fluidized bed reactor (GPR).

With catalyzer, alkane, send into pre-polymerization reactor for body and propylene.To deliver to loop reactor is also simultaneously sent into hydrogen, ethene and added in addition in loop reactor propylene from the polymer slurries of pre-polymerization reactor.

The polymer slurries of self-loop reactor is delivered to GPR with ethene, hydrogen and propylene that other adds in the future.The polymkeric substance that forms is separated after shifting out from GPR with unreacted monomer.

Described catalyzer is punched in the loop reactor according to United States Patent (USP) 5385992 chargings and with propylene.Described pre-polymerization reactor mean residence time of operation and catalyzer under the pressure of 51 crust and 20 ℃ temperature is 7 minutes.

Described loop reactor is operated under the temperature of 50 bar pressures and 75 ℃, and the mean residence time of catalyzer is 1 hour.By the control hydrogen feed MFR (2.16kg, 230 ℃) of the polypropylene unregulated polymer produced in the loop reactor is adjusted to 4.By the control ethylene feed ethylene content is adjusted to 3.8% (weight).

The polymer slurries of self-loop reactor is transferred to first GPR in the future.First GPR reactor is operated under the partial pressure of propylene of 29 total pressures of clinging to and 21 crust.Its service temperature is that the mean residence time of 80 ℃ and catalyzer is 1.2 hours.The MFR (2.16kg, 230 ℃) of the polypropylene unregulated polymer that described GPR produces is adjusted to 2.5 by the dividing potential drop of control hydrogen.Ethylene content is set to 8% (weight) by the dividing potential drop of turnout ratio between the conditioned reaction device and ethene.

Required character is 1% at pre-polymerization reactor, loop reactor be 45% and GPR obtain under 55% the turnout ratio.

Polymkeric substance from described GPR can be transferred among another GPR, produces softer polypropylene copolymer by have higher ethylene partial pressure in second GPR.

Embodiment 13

Use the pilot plant of operation continuously to produce the polypropylene copolymer of the good creeping property of tool.Described equipment comprises catalyzer, alkane, gives body, propylene and ethene feeder system, pre-polymerization reactor, loop reactor and gas fluidized bed reactor (GPR).

With catalyzer, alkane, send into pre-polymerization reactor for body and propylene.To deliver to loop reactor and in loop reactor, send into simultaneously hydrogen and propylene that other adds from the polymer slurries of pre-polymerization reactor.

The polymer slurries of self-loop reactor is delivered in monomer and the isolating flash tank of polymkeric substance in the future.To deliver to GPR from the polymkeric substance of flash tank.To after removing hydrogen, deliver to GPR from the propylene of flash tank.Ethene, the hydrogen that adds in addition and the propylene that adds are in addition delivered to GPR.

Used catalyzer is high activity and the stereospecific ZN-catalyzer according to United States Patent (USP) 5234879 preparations.Before being sent to pre-polymerization reactor, with described catalyzer and triethyl aluminum (TEA) and dicyclopentyl dimethoxyl silane (DCPDMS) (the Al/Ti ratio is 140, and Al/Do is 10 (moles)) contact.

Described loop reactor is operated under the temperature of 50 bar pressures and 75 ℃, and the mean residence time of catalyzer is 1 hour.By the control hydrogen feed MFR (2.16kg, 230 ℃) of the polypropylene unregulated polymer produced in the loop reactor is adjusted to 10.

Described GPR reactor is operated under the partial pressure of propylene of 29 total pressures of clinging to and 16 crust.Its service temperature is that the mean residence time of 80 ℃ and catalyzer is 1.1 hours.The MFR (2.16kg, 230 ℃) of the polypropylene copolymer that described GPR produces is adjusted to 5 by the dividing potential drop of control hydrogen with by the turnout ratio between controlling reactor.Ethylene content is adjusted to 3.5% (weight) by the dividing potential drop of turnout ratio between controlling reactor and ethene.

Required character is 1% at pre-polymerization reactor, be 40% and be to obtain under 59% the turnout ratio at GPR at loop reactor.

Can will transfer among another GPR, provide the polypropylene copolymer of better shock feature by higher ethylene partial pressure production among second GPR from the polymkeric substance of GPR.

Claims

1. method for preparing propylene copolymer, the step that it comprises is as follows:

-with propylene and comonomer in the presence of the Zn catalyzer, under the temperature and 4000-8000kPa elevated pressure of 60-85 ℃ rising, polymerization at least one slurry-phase reactor and at least one Gas-phase reactor has produced the polymerisate of at least 10 weight % in described Gas-phase reactor

-reclaim the copolymerization product comprise unreacted monomer from slurry-phase reactor; With

-copolymerization product is imported to first Gas-phase reactor, there is not unreacted monomer to loop back in the slurry-phase reactor of Gas-phase reactor front basically.

2. according to the process of claim 1 wherein that slurry-phase reactor operates with preparation random copolymers or terpolymer under 60-75 ℃ temperature.

3. according to the process of claim 1 wherein that slurry-phase reactor operates under 75-85 ℃ temperature.

4. according to the polymerisate that the process of claim 1 wherein from first Gas-phase reactor, in the presence of additional comonomer, carry out once more the copolymerization step and by copolymerization.

5. the process of claim 1 wherein

Temperature is at least 80 ℃;

The polymerisate of at least 40 weight % produces in Gas-phase reactor.

6. according to the method for claim 5, the copolymerization in the presence of comonomer of wherein said polymerisate, thus the polymerisate of the impact property of tool improvement is provided.

7. according to the method for claim 5, wherein said copolymerization with second Gas-phase reactor of first Gas-phase reactor arranged in series in carry out.