CN101048458B - Elastomeric reactor blend compositions - Google Patents

Elastomeric reactor blend compositions Download PDF

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CN101048458B
CN101048458B CN2005800373241A CN200580037324A CN101048458B CN 101048458 B CN101048458 B CN 101048458B CN 2005800373241 A CN2005800373241 A CN 2005800373241A CN 200580037324 A CN200580037324 A CN 200580037324A CN 101048458 B CN101048458 B CN 101048458B
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polymkeric substance
reactor
polymerization
solvent
monomer
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CN101048458A (en
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P·S·拉维尚卡尔
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Disclosed herein are various processes, including but not limited to a continuous process for making an elastomer composition having a Mooney Viscosity (ML (1+4) @ 125 DEG C) of from 16 to 180, the composition including a first polymer and a second polymer, the process comprising: polymerizing a first monomer system that includes propylene and one or both of ethylene and propylene in a solvent using a first catalyst system in a first polymerization zone to provide a first polymer, having 60 wt% or more units derived from propylene, including isotactically-arranged propylene-derived sequences and further having a heat of fusion less than 45 J/g or a melting point less than 105 DEG C or both and a Mooney Viscosity (ML (1+4) @ 125 DEG C) of from I to 45; polymerizing a second monomer system that includes ethylene or an alpha-olefin, or both, in a solvent using a second catalyst system in a second polymerization zone to provide a second polymer which is an elastomeric polymer that is either non-crystalline or has ethylene-derived crystallinity; combining the first polymer and the second polymer in a mixture that includes solvent and unreacted monomer; and removing solvent from the mixture to provide an elastomer composition that having a Mooney Viscosity (ML (1+4) @ 125 DEG C) of from 16 to 180.

Description

Elastomeric reactor blend compositions
The cross reference of related application
60/645,138 the rights and interests that the application requires the sequence number 60/618,301 that proposed on October 13rd, 2004 and proposed on January 20th, 2005, the disclosure of these two pieces of applications is introduced for reference.
Background
Invention field
The continuation method that the application relates to elastomeric reactor blend compositions and is used to prepare the elastic composition that comprises first polymkeric substance with different level of crystallization and/or type and second polymkeric substance.
Description of related art
Embodiment of the present invention relate to elastomeric reactor blend compositions.People are constantly making great efforts to prepare has ideal performance and attribute equilibrated polymer composition, to obtain can be used for the enhanced composition of many application.Depend on the concrete application and the concrete blend of expection, itself can show this composition enhancing by many modes.This enhancing including, but not limited to (1) such as grind, extrude, processing characteristics in the technology calendering and the injection moulding under melt; (2) the initial physical performance under solid-state, for example toughness, viscosity, bounding force, tear strength, stretching and elongation; (3) if solidify or sulfuration the improvement of solidification rate and state; (4) as at high temperature keep for example thermal ageing of determined long-term physicals by this physicals.Proposed the polymer composition that the whole bag of tricks obtains to have desired properties and attribute, but these methods have many shortcomings.
US patent No.6,635,715 disclose the ethylene-propylene elastomeric with low-level isotaxy degree of crystallinity of the high crystalline polypropylene type polymkeric substance that contains different amounts.These blends prepare by the various components of physical blending.
US patent No.6,329,477 disclose in the production of the polymer composition that uses bicyclic pentadiene metalloid cyclopentadienyl catalyst and have used tandem reactor, but described composition does not contain two kinds of polymkeric substance with remarkable different propylene contents.Relating to other patent of producing polymer composition is US patent Nos.6,319,998 and 6,207,756.
WO98/02471 and US patent No.6,545,088 disclose using monocyclopentadienyl metalloid cyclopentadienyl catalyst to produce in the EP rubber and have used tandem reactor.
WO 03/040201 discloses the tandem reactor operation of using non-metallocene class catalyzer, has the polymer composition of different crystallinity with production.Hint makes molecular weight etc. be suitable for the recirculation of industrial elastomeric application or the operate continuously method of processing conditions.
Other background technology reference comprises US patent No.6,747,114, and the US patent application discloses 2004/198913, WO 1997/36942 and WO 2002/34795.
The objective of the invention is the development of new polymer composition, wherein the benefit of utilizing series connection and/or parallel reactor to operate provides the useful elastomerics of the total mooney viscosity with 16-180, and use tandem reactor recirculation, polymkeric substance with different crystallinity (isotactic propylene type, ethylene type or unbodied fully) also is provided in said composition simultaneously.Also have, the purpose of this invention is to provide the continuous multiple reactor processing condition that this polymer composition is effectively prepared with technical scale.
General introduction
The invention discloses several different methods, comprise, but be not limited to prepare the mooney viscosity (continuation method of the elastic composition of ML (@125 ℃ of 1+4)) with 16-180, said composition comprises first polymkeric substance and second polymkeric substance, this method comprises: in first polymeric area, use first catalyst body to tie up to polymerization in the solvent and comprise one or both first monomer system in propylene and ethene and the propylene, so that first polymkeric substance to be provided, this first polymkeric substance has 60wt% or more by the unit of propylene derived, comprises the sequence of the propylene derived that isotaxy is arranged and further has the melting heat that is lower than 45J/g or be lower than 105 ℃ fusing point or possess the mooney viscosity (ML (1+4)) of these two kinds of attributes and 1-45 simultaneously; In second polymeric area, use second catalyst body to tie up to that polymerization comprises ethene or alpha-olefin or second monomer system of the two in the solvent, so that second polymkeric substance to be provided, this second polymkeric substance is amorphous or elastomer polymer with the degree of crystallinity that comes from ethene; This first polymkeric substance and second polymkeric substance are merged in the mixture that comprises solvent and unreacted monomer; And from this mixture, remove and desolvate, so that the elastic composition of the mooney viscosity (ML (1+4)) with 16-180 to be provided.
The invention discloses several different methods, the continuation method that contains the elastic composition of first polymkeric substance and second polymkeric substance including, but not limited to preparation, this method comprises: in first polymeric area, use first catalyst body to tie up to polymerization in the solvent and comprise one or both first monomer system in propylene and ethene and the propylene, so that first polymkeric substance to be provided, this first polymkeric substance has 60wt% or more unit by propylene derived, comprises the sequence of the propylene derived that isotaxy is arranged; In second polymeric area, use second catalyst body to tie up to that polymerization comprises ethene or alpha-olefin or second monomer system of the two in the solvent, so that second polymkeric substance to be provided, this second polymkeric substance is an elastomerics and amorphous or have the degree of crystallinity that comes from ethene; This first polymkeric substance and second polymkeric substance are merged in the mixture that comprises solvent and unreacted monomer; From this mixture, remove and desolvate, so that elastic composition to be provided; And with propylene and vinyl monomer and solvent recycled; Wherein this first polymerization proceeds to propylene monomer is depleted to and is lower than preparation this second polymkeric substance required level; This second polymerization and recirculation proceed to vinyl monomer reduced to and are lower than preparation this first polymkeric substance required level, and add other additional propylene monomer for first polymerization, and add other make-up ethylene monomer for second polymerization.This method can be used as tandem reactor or parallel reactor design.
The invention also discloses multiple-stage reactor system, comprise the multiple-stage reactor system that is used to prepare the elastic composition that contains first polymkeric substance and second polymkeric substance, this system comprises: (a) form first polymeric area of first polymkeric substance, this first structure has at least one import that is used to receive first monomer mixture and solvent and at least one is used to distribute the outlet of first effluent that contains first polymkeric substance; (b) form second polymeric area of second polymkeric substance, it has at least one import that is used to receive second monomer mixture and solvent and at least one is used to distribute the outlet of second effluent that contains second polymkeric substance; (c) be used to receive container or other district of the effluent that contains solvent, unreacted monomer, first polymkeric substance and second polymkeric substance; (d) be used for that effluent is incorporated into first of this second structure from this first structure and flow out owner's pipeline, make this reactor assembly can use this effluent Trunk Line to operate with series system; (e) be used to make this first effluent to walk around the first effluent bypass line of this second reactor, make this reactor assembly can use this effluent bypass line to operate with parallel way; (f) be used for effluent is incorporated into from this second structure the second effluent pipeline of the 3rd structure.
The multiple-stage reactor system that is used to prepare the elastic composition that contains first polymkeric substance and second polymkeric substance is also disclosed, this system comprises: (a) form first polymeric area of first polymkeric substance, this first structure has at least one import that is used to receive first monomer mixture and solvent and at least one is used to distribute the outlet of first effluent that contains first polymkeric substance; (b) form second polymeric area of second polymkeric substance, this second structure has at least one import that is used to receive second monomer mixture and solvent and at least one is used to distribute the outlet of second effluent that contains second polymkeric substance; (c) be used to receive container or other district of the effluent that contains solvent, unreacted monomer, first polymkeric substance and second polymkeric substance; (d) effluent that is designed to contain solvent and unreacted monomer is incorporated into first polymeric area of this first polymeric area or second polymeric area or serial or parallel connection and the recirculation line in second polymeric area.
Brief Description Of Drawings
Fig. 1 has illustrated example of the reactor design that can move with tandem reactor or parallel reactor mode.
Describe in detail
Being elaborated now, at first is various definition and performance, summarizes subsequently specific embodiments, and they some are reflected in the claims, then discuss separately some aspect of desired method.
A. definition, performance and test procedure
With the employed various terms of this paper that given a definition. Even the term that does not below have definition to use in the claims, but it should be given one of ordinary skill in the art for the widest given definition of this term, as reflecting at least a printed publication (for example dictionary or article), granted patent or open application.
For convenience's sake, indicate that many special test programs measure performances such as molecular weight, Mooney viscosity, polydispersity (MWD). Yet, when those of ordinary skill is read this patent and is wished to determine whether composition or polymer have the particular characteristic of indicating in the claims, can measure this performance according to any method or test program open or that generally acknowledge so, but the program of specially indicating is preferred. Each claim should be considered to cover the result of any this program, even distinct program may obtain different results or measured value. Therefore, those of ordinary skills can be expected at the experiment variation of the measurement performance that reflects in claims. With regard to the character of substantially method of testing, all numerical value can be considered to " approximately " or " being similar to " setting,
Continuously.When an aspect that is used for described method or method for example during processing step, term " continuously " and derivative thereof comprise that " continuously " should cover continuous supply and discharge reagent and reaction product, the feasible any method or the step that can reach stable state, stopping reaction condition.
Noncrystalline.Term " noncrystalline " should be meant atactic or unbodied, should get rid of isotaxy or syndiotaxy (as other local institute definition of this paper), also should not get rid of having to have under the annealed situation and can measure fusing point (use DSC program) or produce any material that to measure fusing point after the week (168 hours) of annealing.
Polymkeric substance.Except specific context is desired, term " polymer " used herein " be the product of in specific aggregation district or reactor, producing by specific successive polymerization.
Polymerization.Term as used herein " polymerization " should be given those skilled in the art's the wideest employed implication when expression is polymkeric substance with conversion of monomer.Polymeric area is meant the polymeric zone takes place that general the back-mix reactor of random polymkeric substance is formed by being used to form basically.
Polymerization ratio of division (polysplit).Term as used herein " polymerization ratio of division " should be meant the calculation result of the weight of first polymkeric substance of being produced by first polymeric area (propene polymer) divided by the gross weight of first polymkeric substance and second polymkeric substance (ethene polymers).This same definition is suitable for series connection and parallel reactor configuration equally.That is to say that propene polymer always is considered to molecule.
Fusing point, melting heat and crystallization.Polymkeric substance as herein described and composition can characterize with their fusing point (Tm) and melting heat, and described performance can be subjected to comonomer or hinder the influence of the existence of the steric hindrance impurity that crystallite forms by polymer chain.These performances can pass through that dsc (DSC) is used ASTM E-794-95 (modification of E-794-01) program or at US patent No.6,747,114, the 8th hurdle, 14-31 capable in disclosed program measure, this patent is introduced for reference thus in full.
Co-monomer content.The co-monomer content of polymkeric substance and sequence distribute and can use 13C nuclear magnetic resonance spectrometry (NMR) is measured by well known to a person skilled in the art method.The co-monomer content of discrete molecules weight range can use the method for well known to a person skilled in the art to measure, comprise combining of fourier transform infrared spectroscopy (FTIR) and GPC, as at Wheeler and Willis, Applied Spectroscopy, 1993, the 47th volume, described in the 1128-1130 page or leaf.For containing the propylene-ethylene copolymers that is higher than the 75wt% propylene, the co-monomer content of this polymkeric substance (ethylene content) can followingly be measured: at the thin and film uniformly of about 150 ℃ or higher temperatures system, and it is installed on the Perkin Elmer PE1760 infrared spectrophotometer.The record sample from 600cm -1To 4000cm -1Whole spectrum, can calculate the monomer weight percentage of ethene according to following equation: ethene wt%=82.585-111.987X+30.045X 2, wherein X is at 1155cm -1The place peak height with at 722cm -1Or 732cm -1The ratio of the peak height at place's (at will which is higher).For the propylene-ethylene copolymers with 75wt% or lower propylene content, this comonomer (ethene) content can use in the program described in Wheeler and the Willis to be measured.
Tacticity.Term " tacticity " is meant in the polymkeric substance taxis from the orientation of the methyl residue of propylene." the triad tacticity " of polymkeric substance as herein described can be as at US patent No.5,504,172 and US patent No.6, the 642,316, the 6th hurdle the 38th row to described in the 9th hurdle the 18th row by this polymkeric substance 13C nucleus magnetic resonance (NMR) spectrum is measured; These patents are introduced for reference thus in full.
Multi-olefin content.The amount that is present in the polyene hydrocarbon in the polymeric constituent can be present in side in the polymkeric substance after the polymerization by quantitative measurment and hang the amount of free olefin and infer.Several programs for example iodine number and usefulness have been established 1H or 13C NMR measures olefin(e) centent.At polyene hydrocarbon is under the particular case of ENB, and the amount that is present in the polyene hydrocarbon in the polymkeric substance can use ASTM D 3900 to measure.The amount of polyene hydrocarbon is that benchmark is represented with the unitary gross weight of (for example) ethene and propylene derived.
The tacticity index.Here the tacticity index that is expressed as " m/r " can pass through 13C nucleus magnetic resonance (NMR) is measured.Tacticity exponent m/r can be as at H.N.Cheng, Macromolecules, defined such mensuration in 17,1950 (1984).
Isotaxy, syndiotaxy and atactic.Term as used herein " atactic " is defined as being meant any polymkeric substance of tacticity index 2.0-4.0.Term as used herein " syndiotaxy " is defined as being meant that the tacticity index is any polymkeric substance of 1.0 to (but not comprising) 2.0.Term as used herein " isotaxy " is defined as being meant that the tacticity index is greater than any polymkeric substance of 4.0.
Molecular weight characteristics.Various molecular weight characteristics of polymeric constituent as herein described (or polymkeric substance) (for example Mw and Mn) and molecular weight distribution mw/mn (MWD) can be according at US patent No.6,525, disclosed program determination during 157 the 5th hurdle 1-44 is capable, this patent are introduced for reference thus in full.
Mooney viscosity.Term " mooney viscosity " is the term that is used to characterize some polymkeric substance, polymeric constituent and polymer composition here.The term as used herein mooney viscosity (ML (@125 ℃ of 1+4)) or write a Chinese character in simplified form " mooney viscosity " according at US patent No.6, definition described in 686,415 and process of measurement define and measure; This patent is introduced for reference thus in full, especially the text in the 6th hurdle the 59th row is gone to the 7th hurdle the 59th.Alternatively, any " mooney viscosity " value of mentioning here (comprise in the claims those) is regarded as comprising any mooney viscosity any generally acknowledged, disclosed program determination according to being used to measure mooney viscosity.
Term as used herein " MFR " expression " melt flow rate (MFR) ", and be used for characterize polymers, component and composition.The unit of " MFR " is gram/10 minutes, is used to measure the test of MFR here to carry out in any modification described in the ASTM-1238 and condition (under 230 ℃, using 2.16kg).
Intermolecular solubleness and composition distribute.Other characteristic that may mention in some claim is " intermolecular solubleness distribution " and " intermolecular composition distribution ".Also have, especially for some embodiment of described first polymkeric substance, this paper employed " uniform distribution " be defined as that multipolymer is formed and the intermolecular statistics of two kinds of distributions of the tacticity of polypropylene on do not have marked difference.The definition of these terms and the mode of calculating them are disclosed in US patent No.6, during capable and the 10th hurdle 16-53 of 525,157 the 9th hurdle 30-41 is capable; Described patent is introduced for reference thus in full.
B. the specific embodiments of method and composition
Below set forth specific embodiments, they some also are included in the claim.Each claims has defined an independent invention, and when infringement was judged, it was believed to comprise the various key elements stipulated or the equivalent of qualification in described claim.Depend on context, below all " inventions " of mentioning can only be meant some specific embodiments in some cases.In other cases, should be realized that " invention " mentioned is meant one or multinomial, but may not be the theme described in whole claims.Below illustrate in greater detail each invention, comprise specific embodiments, modification and embodiment, but the invention is not restricted to these embodiments, modification or embodiment, their purpose is to make those of ordinary skills realize and to utilize the present invention in conjunction with the information in this patent and obtainable information and technology.
In above or other local described any method, solvent of removing from described mixture and unreacted monomer can be recycled to first polymeric area or second polymeric area, or first polymeric area and second polymeric area are in the two.
In above or other local described any method, in the process of recirculation, before being incorporated into first or second polymeric area, can separate described solvent and unreacted monomer to small part.
In above or other local described any method, described first polymkeric substance for example can have the mooney viscosity (ML (1+4)) of 16-180 and be lower than the melting heat of 45J/g or be lower than 105 ℃ fusing point or possess this two kinds of attributes simultaneously, and described second polymkeric substance has the mooney viscosity (ML (1+4)) of 1-45.
In above or other local described any method of this paper, described second polymkeric substance for example can be the random copolymers of ethene and propylene.
In above or other local described any method of this paper, at least a portion of the effluent of described first polymeric area can be incorporated in second polymeric area continuously.
In above or other local described any method of this paper, at least a portion of the effluent of described first polymeric area can merge with the effluent of second polymeric area.
In above or other local described any method of this paper, described first and second polymeric areas can be changed into the parallel operation mode from the serial operation mode, perhaps change into the serial operation mode by the parallel operation mode, perhaps with these two kinds of operating method operations.
In above or other local described any method of this paper, described polymerization ratio of division can for example be 5-95.
In above or other local described any method of this paper, described composition can be to have the polymerization ratio of division of 5-35, the mooney viscosity of 16-100 (the modification EP rubber of ML (@125 ℃ of 1+4)) and 30-80wt% ethylene content.
In above or other local described any method of this paper, described composition can be to have the polymerization ratio of division of 65-95, the mooney viscosity of 16-45 (the modified propylene elastomerics of the ethylene content of ML (@125 ℃ of 1+4)) and 25-50wt%.
In above or other local described any method of this paper, described first polymkeric substance and second mixture of polymers of containing can be assigned to post-treatment to form pellet or packing material (bale) by devolatilization, reclaim unreacted monomer and solvent, and they are recycled to first and second polymeric areas, perhaps these two polymeric areas.
More than or other local described any method of this paper for example may further include recirculation propylene and vinyl monomer and solvent, wherein carry out described first polymerization so as with propylene monomer be consumed to be lower than the preparation the second polymkeric substance desired level level, wherein carry out second polymerization and recirculation so as with vinyl monomer be reduced to be lower than the preparation the first polymkeric substance desired level level, and add the additional propylene monomer that replenishes and be used for first polymerization, add additional make-up ethylene monomer and be used for second polymerization.
More than or other local described any method of this paper for example may further include recycle stream be provided, wherein, the mark of first polymkeric substance of being produced and the mark of second polymkeric substance are independently by cutting apart from the amount that supplies to the first and second polymeric solvents of recirculation with by providing additional fresh feed to control to change flow and each polymeric heat-removal capability, this first is aggregated under the temperature of the fusing point that is lower than first polymkeric substance and carries out, and this second is aggregated in than carrying out under the temperature that is used for high 20-200 ℃ of the first polymeric temperature.
In other local described any method of above or this paper, can use transfer agent for example hydrogen come the restriction molecule amount.
Whether in other local described any reactor assembly of above or this paper, adopting parallel way can be sensitive corresponding to preselected polymerization ratio of division to determining the polymerization ratio of division.
In above or other local described any reactor assembly of this paper, adopting parallel way can be sensitive to the propylene content of determining propene polymer.
In above or other local described any method of this paper, changing into parallel way from series system for example can the sensitive ethylene content of determining reactor blend compositions.
In above or other local described any method of this paper, when polymerization ratio of division during, preferably use parallel way more than or equal to the C3C2 coefficient of the calculating summation (calculated combination) that constitutes FPP (the first polymkeric substance propylene content) and BPE (blend polymkeric substance ethylene content).
In other local described any method of above or this paper, when the polymerization ratio of division greater than 575* (100-FPP) 0.14* (BPE) -0.81The time, preferably use parallel way, wherein FPP is propylene content (wt% of propene polymer), BPE is the ethylene content of tandem reactor blend composition or parallel reactor blend composition.
More than or other local described any method of this paper can comprise in addition this recycle stream is divided into first recycle stream and second recycle stream, this first recycle stream is incorporated into first polymeric area and this second recycle stream is incorporated into second polymeric area.
More than or other local described any method of this paper can comprise in addition most recycle stream is incorporated into second polymeric area.
More than or other local described any method of this paper can comprise in addition and select to be enough to obtain (i) required second polymerization temperature; Or the amount of the solvent in second recycle stream of (ii) required polymerization ratio of division.
In above or other local described any method of this paper, from described mixture, remove and desolvate and unreacted monomer can comprise that (i) allows this mixture carry out first separating step, so that first materials flow (it can also be defined as the materials flow of the first polymkeric substance poorness, does not preferably contain or contain polymkeric substance seldom) and first materials flow of being rich in polymkeric substance of being rich in solvent of extracting from this mixture to be provided; (ii) allow this first materials flow of being rich in polymkeric substance carry out second separating step, so that more spissated second materials flow of being rich in polymkeric substance is provided; The materials flow of (iii) this being rich in solvent merges, so that the recycle stream of merging to be provided, be used for being fed into first polymeric area or second polymeric area or first polymeric area and second polymeric area the two.This materials flow of being rich in solvent can contain the volatility unreacted monomer equally.Whether this first step can comprise liquid separation or evaporation, no matter heat.Can apply vacuum to this spissated materials flow of being rich in polymkeric substance, to extract last trace solvent and monomer.This can finish by vacuum extraction from the polymer material that stirs.This stirring can provide with film or chain (strand) vaporizer, twin screw extruder or devolatilization LIST device as described elsewhere.
In above or other local described any method of this paper, from described mixture, remove and desolvate and unreacted monomer can comprise that this mixture with at least a portion carries out liquid phase separation (preferably under high pressure), so that the part (poor polymer moieties) that is rich in solvent and lean solvent part (being rich in the part of polymkeric substance) to be provided, the part (for example as recycle stream) that wherein this is rich in solvent is incorporated into first polymeric area or second polymeric area or first and second polymeric areas in the two.
In above or other local described any method of this paper, from described mixture, remove and desolvate and unreacted monomer can comprise this mixture devolatilization with at least a portion, so that part and the lean solvent part that is rich in solvent to be provided, the part that wherein this is rich in solvent is incorporated into first polymeric area or second polymeric area or first and second polymeric areas in the two, for example as the part of recirculation.
In above or other local described any method of this paper, described recycle stream can be incorporated into first polymeric area and second polymeric area, so that a kind of recirculation ratio of division (split) to be provided, wherein this recirculation ratio of division to small part is regulated according to the temperature of first or second polymeric area according to preselected polymerization ratio of division or to small part.
More than or other local described any method of this paper can move by the tandem reactor mode, wherein recycle stream is incorporated into first polymeric area and second polymeric area, so that a kind of recirculation ratio of division to be provided, wherein the recycle stream percentage of supply response device 1 equals 2.8* (PS) 0.67* (RT2/RT1) 1.11, PS=polymerization ratio of division wherein; RT2=second temperature of reactor (℃); With RT1=first temperature of reactor (℃).
More than or other local described any method of this paper can move by the parallel reactor mode, wherein recycle stream is incorporated into first polymeric area and second polymeric area, so that a kind of recirculation ratio of division to be provided, wherein the recycle stream percentage of supply response device 1 equals 4.5* (PS) 0.55* (RT2/RT1) 0.67, PS=polymerization ratio of division wherein; RT2=second temperature of reactor (℃); With RT1=first temperature of reactor (℃).
Composition disclosed herein is total mooney viscosity with 16-180 (ML (@125 ℃ of 1+4)) and be lower than the composition of granular or packing material form of the melting heat of 50J/g, it comprises first polymkeric substance and second polymkeric substance, wherein this first polymkeric substance is to have the unitary content of at least 60% propylene derived and comprise the sequence of the propylene derived that isotaxy is arranged and be lower than the melting heat of 45J/g or be lower than the elastomerics unregulated polymer of 105 ℃ fusing point that this second polymkeric substance is the unitary multipolymer that does not have crystallinity or have crystalline ethene of ethylene type and propylene derived.
In above or other local described some method of this paper, (ML (@125 ℃ of 1+4)) is 16-180 to the mooney viscosity of described composition; Or from any any upper limit of 180 or 140 or 120 that is limited to down of 16 or 20 or 24.
In above or other local described some method of this paper, the MFR of described first polymkeric substance is 0.5-100g/10min; Or from 0.5 0.8 or 1.0g/10min any be limited to down 40 or 30 or any upper limit of 20g/10min.
In above or other local described some method of this paper, the MFR of described reactor blend is 0.05-1.3g/10min; Or from 0.05 0.06 or 0.07g/10min any be limited to down 1.3 or 1.0 or any upper limit of 0.8g/10min.
In above or other local described some method of this paper, the molecular weight of described first polymkeric substance (Mw) is 80000-400,000; Or from 100,000 or 120,000 or 140,000 any under be limited to any upper limit of 400,000 or 350,000 or 300,000.
In above or other local described some method of this paper, the molecular weight of described first polymkeric substance (Mn) is 40,000-200,000; Or from 50,000 or 60,000 or 70,000 any under be limited to any upper limit of 200,000 or 175,000 or 150,000.
In above or other local described some method of this paper, the molecular weight of described composition (Mw) is 60,000-800,000; Or from 60,000 or 90,000 or 120,000 any under be limited to any upper limit of 800,000 or 700,000 or 600,000.
In above or other local described some method of this paper, the molecular weight of described composition (Mn) is 30,000-160,000; Or from 30,000 or 45,000 or 60,000 any under be limited to any upper limit of 160,00 or 140,000 or 120,000.
In above or other local described some method of this paper, the polymolecularity of described first polymkeric substance (Mw/Mn) is 1.8-2.3; Or from any any upper limit of 2.3 or 2.2 or 2.1 that is limited to down of 1.8 or 1.9 or 2.0.
In above or other local described some method of this paper, the polymolecularity of described composition (Mw/Mn) is 1.8-10; Or from any any upper limit of 10 or 6 or 3.5 that is limited to down of 2.2 or 2.0 or 1.8.
In above or other local described some method of this paper, described polymerization ratio of division (amount of first polymkeric substance for preparing in percentile first polymerization as total composition) is 5-95; Or from 5 or 15 or 25 following 95 or 80 or 60 the upper limit that is limited to.
In above or other local described some method of this paper, described first polymkeric substance accounts for the 5-95wt% of total composition.
First and second catalyzer can be identical; Perhaps they can be different, but in certain embodiments, can have identical activator, as being described in more detail in other place of this paper.In above or other local described some method of this paper, first catalyzer and/or second catalyzer can be metalloceness.One more specifically aspect, first and/or second catalyzer is the monocyclopentadienyl compound.First and/or second catalyzer can be a bicyclic pentadiene compounds.The cyclopentadienyl ligands of first and/or second catalyzer can be an indenyl ligands.First and/or second catalyzer can also be a Ziegler-Natta catalyst.First and/or second catalyzer can also be the pyridine amine catalyst.One concrete aspect, first catalyzer can be any catalyzer of mentioning in the open WO 03/040201 of PCT, that especially mentions is supplied to those of first reactor in the double-reactor scheme.Similarly, though second catalyzer can also be any catalyzer of mentioning in the open WO 03/040201 of PCT, more specifically second catalyzer be mention in the tandem reactor configuration, be supplied to those of second reactor.
From generalized aspect, described composition can use any SSC (single-site catalysts) to prepare.This catalyzer can be to contain periodictable 3-10 group 4 transition metal usually; In polymerization process, keep being bonded to the transition metal complex of the assistant ligand of this transition metal with at least one.Preferably, this transition metal uses with reduction positively charged ion state, and stable with promotor or activator.
In other local described any method of above or this paper, described first and second catalyzer are can right and wrong catalyst-loaded.
In above or other local described any method of this paper, can select and use the high alpha-olefin that does not have taxis basically to introduce to described second catalyzer.
In above or other local described some method of this paper, described first catalyzer is a chirality dicyclopentadiene radical derivative, and described second catalyzer is an achirality bridging fluorenyl cyclopentadiene radical derivative.
In above or other local described some method of this paper, described first and second catalyzer are used in combination with non-coordination anion activator, first and second reactors use identical activator, and optional subsidiary have that scavenging agent for example removes usefulness contain the aluminium derivative.
In other local described some method of above or this paper, described non-coordination anion is to have at least two to have condensed ring system, preferred perfluor ring and the boron complexes of the part of four aryl complex most preferably.
Some composition as herein described does not contain or contains the filler that is lower than 5wt% and do not contain or contain the fusing point that is lower than 10wt% and is 〉=110 ℃ isotactic polyprophlene fraction.
In some composition as herein described, described composition has total melting heat of 1-45J/g.
In some composition as herein described, the mooney viscosity of first polymkeric substance is lower than 25 Mooney ML (1+4,125 ℃), than low at least 10 units of Mooney ML (1+4,125 ℃) of total composition.
Unitary combined content in ethene and propylene derived is a benchmark, and some composition as herein described has the unitary total content of the ethylene derivative that is lower than 95wt%.
Some composition as herein described contains 40-60wt%, the unit of the ethylene derivative of preferred 45wt% or 55wt%.
Some composition as herein described has the unit of the ethylene derivative that is lower than 30wt%.
C. multistage polymerization
Reactor blend as herein described is meant and carries out two kinds of (or multiple) different polymerizations (or polymerization stage) forming in " multistage polymerization " continuously.More particularly, multistage polymerization can comprise two or more sequential polymerization (also being called " series connection method "), or two or more parallel polymerization (also being called " and linked method ").
The polymkeric substance that will prepare in each reactor of described continuous multiple reactor solution device is not separated from solvent in advance with the blend of solution form.This blend can be the product of tandem reactor operation, and wherein the effluent of first reactor enters second reactor, and the effluent of second reactor can be transported to the post-processing step that comprises devolatilization.This blend can also be the product of parallel reactor operation, and wherein the effluent of two reactors is merged, and is transported to post-processing step.Any one selection scheme provides the uniform mixing of the polymkeric substance in the devolatilization blend.Any situation all can be made into various polymerization ratio of division, thereby the ratio of the amount of the polymkeric substance of producing in each reactor can change in wide region.
Below discuss first polymkeric substance and second polymkeric substance of anabolic reaction device blend composition, follow, after again be and the linked method part by the series connection method part.Under suitable occasion, series connection and and linked method between corresponding difference will be indicated that otherwise the argumentation of series connection method should be regarded as being suitable for equally and linked method.
D. first polymkeric substance (propene polymer)
As mentioned above, the reactor blend here preferably comprises first polymkeric substance at least, it preferably by first polyreaction (under other local described condition of this paper) and preferably as series connection method or and " first reactor " of the part of linked method in the polymkeric substance of formation.
As described below, first polymkeric substance (also being called " propene polymer " here) should have (minimum) 50wt% propylene units, and is preferably more.First polymkeric substance should be to have 〉=unit by propylene derived of 60wt%, has the sequence of the propylene derived that isotaxy arranges and the propene polymer (preferred polypropylene copolymers) with the melting heat that is lower than 45J/g.First polymkeric substance preferably has the non-propylene co-monomer of 5wt% unit at least, ethylene unit for example, more preferably 10wt% or more ethylene unit at least.First crystallinity of polymer is produced by the isotactic polyprophlene sequence.The degree of isotacticity of first polymkeric substance can be present in the mm triad with dominant propylene residues and comes illustration in the polymkeric substance.
First crystallinity of polymer can be represented with melting heat.First polymkeric substance of the present invention can have any melting heat of passing through DSC mensuration that is limited to any upper limit of 30J/g or 40J/g or 50J/g or 60J/g or 75J/g down of 1.0J/g or 1.5J/g or 3.0J/g or 4.0J/g or 6.0J/g or 7.0J/g.Preferably, the melting heat of first polymkeric substance is lower than 45J/g.Do not wish to accept the restriction of opinion, it is believed that first polymkeric substance generally has the crystallizable propylene sequences of isotaxy, above melting heat is considered to owing to these crystallization segmental fusions.
The first crystallinity of polymer size can also be reflected on its fusing point.Preferably, first polymkeric substance has single fusing point.Yet the copolymerization of propylene matter sample has usually shown the secondary melting peak adjacent with this main peak.The climax is considered to fusing point.First polymkeric substance as herein described can have the fusing point that DSC measures that passes through of any lower limit of being limited to 0 ℃ or 20 ℃ or 25 ℃ or 30 ℃ or 35 ℃ or 40 ℃ or 45 ℃ on 115 ℃ or 110 ℃ or 105 ℃ or 90 ℃ or 80 ℃ or 70 ℃ any.Preferably, first polymkeric substance has and is lower than 105 ℃, more preferably less than 100 ℃, even more preferably less than 90 ℃ fusing point.Also have, preferably, first polymkeric substance has the fusing point that is higher than about 25 ℃ or 40 ℃.
For first polymkeric substance, at least 75wt% or at least 80wt% at least 85wt% or at least 90wt% at least 95wt% or at least 97wt% or at least this polymkeric substance of 99wt% dissolve in the single temperature fraction, or dissolve in two adjacent temperature fractions, this polymkeric substance of remainder dissolve in followed by a previous or back temperature fraction in.These percentage are for example fractions in hexane that begin under 23 ℃, and follow-up fraction is the fraction under the temperature that increases with about 8 ℃ increment more than 23 ℃.Satisfy this classification requirement and mean that the tacticity of the polypropylene of polymkeric substance has no significant intermolecular difference on the statistics.
In certain embodiments, as determined with the method for measuring the triad tacticity, the percentage of the mm triad in first polymkeric substance has any upper limit of 98% or 95% or 90% or 85% or 82% or 80% or 75% and any lower limit of 50% or 60%.
Some first polymkeric substance has greater than 0%, or 50% or 25% any on be limited to isotacticity index in any lower range of 3% or 10%.
The tacticity of some first polymkeric substance (m/r) can have any upper limit of 800 or 1000 or 1200, and these polymkeric substance can have any lower limit of 40 or 60.
As described below, first polymerization (and second polymerization) can be carried out in the presence of alpha-olefin in some cases; Like this, formed polymkeric substance comprises by this alpha-olefin " deutero-unit " when having this alpha-olefin.Identical alpha-olefin or different alpha-olefins can be incorporated in first and second polymerizations.Usually, this alpha-olefin preferably has 3-10 carbon atom.The particular instance of these alpha-olefins is C 3-C 20Alpha-olefin is including, but not limited to propylene; Butene-1; Amylene-1; 2-methylpentene-1; 3-methyl butene-1; Hexene-1; 3-methylpentene-1; 4-methylpentene-1; 3,3-neohexene-1; Heptene-1; Hexene-1; Methyl hexene-1; Dimethyl pentene-1; The trimethylammonium butene-1; Ethypentene-1; Octene-1; Methylpentene-1; Neohexene-1; 2,4,4-Trimethyl-1-pentene-1; Ethyl hexene-1; Methylethyl amylene-1; Diethyl hexene-1; Propyl group amylene-1; Decylene-1, the methyl nonylene-1; Nonylene-1; Dimethyl octene-1; Trimethylammonium heptene-1; The ethyl octene-1; The methylethyl butene-1; Diethyl hexene-1; Dodecylene-1 and cetene-1.
First polymkeric substance can be chosen wantonly and comprise polyene hydrocarbon.Should optional polyene hydrocarbon can be any hydrocarbon structure with at least two unsaturated link(age)s, wherein at least one unsaturated link(age) be introduced in the polymkeric substance easily.Second key can the subparticipation polymerization, forms long chain branches, but follow-up curing or at least some unsaturated link(age)s of sulfurized that are suitable in the post polymerization method preferably are provided.The example of optional polyene hydrocarbon comprises, but be not limited to divinyl, pentadiene, hexadiene (for example 1, the 4-hexadiene), heptadiene (for example 1,6-heptadiene), octadiene (for example 1,7-octadiene), nonadiene (for example 1, the 8-nonadiene), decadiene (for example 1,9-decadiene), 11 carbon diene (for example 1,10-11 carbon diene), 12 carbon diene (for example 1,11-12 carbon diene), oleatridecadiene (for example 1,12-oleatridecadiene), 14 carbon diene (for example 1,13-14 carbon diene), 15 carbon diene, 16 carbon diene, 17 carbon diene, 18 carbon diene, 19 carbon diene, 20 carbon diene, 21 carbon diene, 22 carbon diene, two oleatridecadienes, the tetracosa carbon diene, 25 carbon diene, 26 carbon diene, heptacosadiene, 28 carbon diene, 29 carbon diene, 30 carbon diene and molecular weight (Mw) are lower than the polybutadiene of 1000g/mol.The example of straight chain acyclic dienes is including, but not limited to 1,4-hexadiene and 1,6-octadiene.The example of side chain acyclic dienes is including, but not limited to the 5-methyl isophthalic acid, 4-hexadiene, 3,7-dimethyl-1,6-octadiene and 3,7-dimethyl-1,7-octadiene.The example of the alicyclic diene of monocycle is including, but not limited to 1, and 1,5-cyclooctadiene and 1,7-encircle 12 carbon diene.The example of many alicyclic condensed ring of ring and bridging cyclic diene is including, but not limited to tetrahydroindene; Norbornadiene; The methyl tetrahydroindene; Dicyclopentadiene (DCPD); Dicyclo-(2.2.1)-heptan-2, the 5-diene; And thiazolinyl-, alkylidene-, cycloalkenyl group-and ring alkylidene norbornylene [comprise for example 5-methylene-2-norbornene, 5-ethidine-2-norbornylene, 5-propenyl-2-norbornylene, 5-isopropylidene-2-norbornylene, 5-(4-cyclopentenyl)-2-norbornylene, 5-cyclohexylidene base-2-norbornylene and 5-vinyl-2-norbornylene].The example of the alkene that cycloalkenyl group replaces is including, but not limited to vinyl cyclohexene, allyl group tetrahydrobenzene, vinyl cyclooctene, 4 vinyl cyclohexene, allyl group cyclodecene, ethene basic ring dodecylene and Fourth Ring (A-11,12)-5,8-dodecylene.
Any first polymkeric substance that contains ethene preferably has no remarkable intramolecularly composition difference on the statistics, and this composition is the propylene of the segment (intramolecularly) along same chain and the ratio of ethene.This compositional analysis is inferred out by the method that is used for synthetic these polymkeric substance, can also be passed through 13CNMR measures, and it has been located with respect to the comonomer residue of adjacent propylene residues and propylene and has inserted mistake.
First polymkeric substance also preferably has no remarkable intramolecularly tacticity difference on the statistics, and this is owing to segment (intramolecularly) the isotaxy orientation of propylene units along same chain.This compositional analysis is inferred out that described analysis comprises dsc, electron microscope and relaxation mensuration by the result of following detailed analysis.Have in tacticity under the situation of remarkable intramolecularly difference, formed " stereoblock " structure as described below, the number of isotactic propylene residue wherein adjacent one another are is more much bigger than statistics.In addition, the fusing point of these polymkeric substance depends on degree of crystallinity, because the polymkeric substance of more obvious block-wise should have higher fusing point and the solubleness in the room temperature solvent reduces.
E. second polymkeric substance (ethene polymers)
Reactor blend as herein described comprises second polymeric constituent (second polymkeric substance), it preferably (or comprising) have above 30wt% or 40wt% or 50wt% by the unitary elastomerics of vinyl monomer deutero-.Second crystallinity of polymer and therefore other performance preferably be different from those of first polymkeric substance.
Preferably, second polymkeric substance (also being called " ethene polymers ") is amorphous, atactic or unbodied for example, but in certain embodiments, second polymkeric substance is crystalline (comprising " hypocrystalline ").But any degree of crystallinity of second polymkeric substance preferably derives from ethene, and whether the degree of crystallinity that many disclosed methods, program and technology can be used to estimate certain material derives from ethene.By from composition, removing first polymkeric substance and measuring residual second crystallinity of polymer then, second crystallinity of polymer and first crystallinity of polymer can be made a distinction.This degree of crystallinity of being measured uses the degree of crystallinity of ceridust to calibrate and be associated with co-monomer content usually.Degree of crystallinity percentage under these situations is measured as the percentage of ceridust degree of crystallinity, and determines that thus degree of crystallinity derives from ethene.
Preferably, except unit by ethylene derivative, second polymkeric substance also comprises by 'alpha '-olefin monomers deutero-unit, in certain embodiments, it is identical with the 'alpha '-olefin monomers that is used to form first polymkeric substance, in other embodiments, is different from the 'alpha '-olefin monomers that is used to form first polymkeric substance to small part, in this case, it is called as " second alpha-olefin ".Can use above any 'alpha '-olefin monomers of in first polymkeric substance, enumerating, especially butene-1, amylene-1, hexene-1, heptene-1 or octene-1.Advantageously, second polymkeric substance can use and be selected from above monomer for different 'alpha '-olefin monomers in the cited monomer of first polymkeric substance and/or different amounts, for example ethene and 'alpha '-olefin monomers are prepared, to prepare the second dissimilar polymkeric substance, for example has the ethylene elastomer of desired properties.Therefore, can prepare blend composition, wherein said composition comprises first polymkeric substance with one group of performance and second polymkeric substance with one group of different performance, and like this, said composition has the expectation mixing or the balance of desired properties.Advantageously, can use continuous multi-stage method (serial or parallel connection) to form said composition, not need to use any separating step, for example except that desolvating, for example not needing physics to merge polymkeric substance by devolatilization or at after separating.
Preferably, second polymkeric substance forms in (or by) second polymerization process, and under the situation of tandem reactor, this preferably carries out at the reactor in the downstream that is arranged in the reactor that carries out first polymerization and form most first polymkeric substance.Comprising that " second polymkeric substance " can form simultaneously with " first polymkeric substance " under situation polymerization in parallel and/or parallel reactor and linked method, but product stream (still comprising solvent) is being merged after fully forming first and second polymkeric substance.
Preferably, second polymkeric substance comprise (or) elastomer polymer, it preferably has the ethene-alpha-olefin elastomerics (comprising ethene-cycloolefin and ethene-alpha-olefin-diolefine) of high molecular (as being measured by mooney viscosity) and low-crystallinity.Second polymkeric substance can be with any suitable catalyzer but is preferably used following Preparation of Catalyst.In at least one specific embodiments, second polymkeric substance forms in the presence of the catalyzer (for example " second catalyzer ") that is different from the catalyzer (for example " first catalyzer ") that is used for polymerization first polymkeric substance.Can form and have many second polymkeric substance of selecting to form (for example monomer type and content) and performance.
A purpose of first polymkeric substance is to improve the characteristic of second polymkeric substance.Depend on the application-specific and the specific blends of expection, this raising can itself embody in many ways.This raising is including, but not limited to the improvement of following aspect: solidification rate and state; As by such as grind, extrude, the defined processing characteristics of method calendering and the injection moulding; Physicals for example toughness, viscosity, bounding force, tear strength, stretching and elongation and as by the defined thermal ageing of this physicals maintenance at high temperature.
For example, at US patent No.6, the ethene described in 376,610, alpha-olefin, vinyl norbornene are elastomeric any, or introducing can be used as second polymer formation as any this elastomerics (mainly being intended for use power cable coating) of the ENB of polyene hydrocarbon.The part that this patent is described described elastomerics, their performance and prepared their method is introduced for reference for the purpose of US patent working thus.
Also have, at US patent No.6, the ethene described in 271,311, alpha-olefin elastomeric polymer composition any, or introducing can be used as second polymer formation as any this elastomerics (it mainly is intended for use to form extruded product) of the ENB of polyene hydrocarbon.The part that this patent is described described elastomerics, their performance and prepared their method is introduced for reference for the purpose of US patent working thus.
In addition, second polymkeric substance can be at US patent No.5, and the ethene described in 807,946, alpha-olefin, vinyl norbornene are elastomeric any, perhaps introduce any this elastomerics as the ENB of polyene hydrocarbon, mainly are intended for use vehicle part.The part that this patent is described described elastomerics, their performance and prepared their method is introduced for reference for the purpose of US patent working thus.
In addition, at US patent No.5, the ethene described in 766,713, alpha-olefin, vinyl norbornene are elastomeric any, or introducing can be used as second polymer formation as any this elastomerics (mainly being intended for use the vehicle flexible pipe) of the ENB of polyene hydrocarbon.The part that this patent is described described elastomerics, their performance and prepared their method is introduced for reference for the purpose of US patent working thus.
Also have, at US patent No.5,698, ethene described in 650, alpha-olefin, vinyl norbornene are elastomeric any, or introducing can be used as second polymer formation as any this elastomerics (mainly being intended for use vehicle brake parts and power transmission belt) of the ENB of polyene hydrocarbon.The part that this patent is described described elastomerics, their performance and prepared their method is introduced for reference for the purpose of US patent working thus.
In addition, at US patent No.5, the ethene described in 656,693, alpha-olefin, vinyl norbornene are elastomeric any, or introducing can be used as second polymer formation as any this elastomerics (having the improvement curing performance) of the ENB of polyene hydrocarbon.The part that this patent is described described elastomerics, their performance and prepared their method is introduced for reference for the purpose of US patent working thus.
Also have, at US patent No.5, the ethene described in 654,370, alpha-olefin, non-conjugated dicyclo diene elastomer polymkeric substance any, or introduce any this elastomerics as the ENB of polyene hydrocarbon (its then can compounding and calendering be sheet material), can be used as second polymer formation.The part that this patent is described described elastomerics, their performance and prepared their method is introduced for reference for the purpose of US patent working thus.
At last, at US patent No.5, the ethene described in 571,883, alpha-olefin, vinyl norbornene are elastomeric any, or introducing can be used as second polymer formation as any this elastomerics (it can be used to form Motor vehicles vibration damping parts) of the ENB of polyene hydrocarbon.The part that this patent is described described elastomerics, their performance and prepared their method is introduced for reference for the purpose of US patent working thus.
Therefore, as giving an example in above patent, second polymkeric substance can comprise the polyene hydrocarbon that one or more are optional, especially comprises diolefine; Therefore, second polymkeric substance can be ethylene-propylene-diene copolymer (being commonly referred to " EPDM ").The polyene hydrocarbon that should choose wantonly is considered to have any hydrocarbon structure of at least two unsaturated link(age)s, and wherein at least one unsaturated link(age) is introduced in the polymkeric substance easily.Second key can the subparticipation polymerization, forming long chain branches, but preferably provides follow-up curing or at least some unsaturated link(age)s of sulfurized that are suitable in the post polymerization method.The example of optional polyene hydrocarbon comprises, but be not limited to divinyl, pentadiene, hexadiene (for example 1, the 4-hexadiene), heptadiene (for example 1,6-heptadiene), octadiene (for example 1,7-octadiene), nonadiene (for example 1, the 8-nonadiene), decadiene (for example 1,9-decadiene), 11 carbon diene (for example 1,10-11 carbon diene), 12 carbon diene (for example 1,11-12 carbon diene), oleatridecadiene (for example 1,12-oleatridecadiene), 14 carbon diene (for example 1,13-14 carbon diene), 15 carbon diene, 16 carbon diene, 17 carbon diene, 18 carbon diene, 19 carbon diene, 20 carbon diene, 21 carbon diene, 22 carbon diene, two oleatridecadienes, the tetracosa carbon diene, 25 carbon diene, 26 carbon diene, heptacosadiene, 28 carbon diene, 29 carbon diene, 30 carbon diene and molecular weight (Mw) are lower than the polybutadiene of 1000g/mol.The example of straight chain acyclic dienes is including, but not limited to 1,4-hexadiene and 1,6-octadiene.The example of side chain acyclic dienes is including, but not limited to the 5-methyl isophthalic acid, 4-hexadiene, 3,7-dimethyl-1,6-octadiene and 3,7-dimethyl-1,7-octadiene.The example of the alicyclic diene of monocycle is including, but not limited to 1, and 1,5-cyclooctadiene and 1,7-encircle 12 carbon diene.The example of many alicyclic condensed ring of ring and bridging cyclic diene is including, but not limited to tetrahydroindene; Norbornadiene; The methyl tetrahydroindene; Dicyclopentadiene (DCPD), dicyclo-(2.2.1)-and heptan-2, the 5-diene; And thiazolinyl-, alkylidene-, cycloalkenyl group-and ring alkylidene norbornylene [comprise for example 5-methylene-2-norbornene, 5-ethidine-2-norbornylene, 5-propenyl-2-norbornylene, 5-isopropylidene-2-norbornylene, 5-(4-cyclopentenyl)-2-norbornylene, 5-cyclohexylidene base-2-norbornylene and 5-vinyl-2-norbornylene].The example of the alkene that cycloalkenyl group replaces is including, but not limited to vinyl cyclohexene, allyl group tetrahydrobenzene, vinyl cyclooctene, 4 vinyl cyclohexene, allyl group cyclodecene, ethene basic ring dodecylene and Fourth Ring (A-11,12)-5,8-dodecylene.
F. series connection method
As mentioned above, a kind of form of multistage polymeric is series connection method (for example, a tandem reactor method).Preferably, in comprising the series connection method of sequential polymerization, two (or a plurality of) reactors are by conduit (for example pipeline) " series connection " connection each other, make the material (for example effluent) of discharging be fed into another reactor, though can mounted valve or other assembly between these two reactors from a reactor.Sometimes, these two (or a plurality of) tandem reactors are called as single " tandem reactor ".
Preferably, described series connection method is to comprise the continuous solution polymerization method of material being introduced continuously the order equipment group (tandem reactor) of passing through reactor.This reactor apparatus group comprises the polymerization reactor that at least two series connection (in proper order) connect, wherein preparation in each comfortable independent reactor of first polymkeric substance and second polymkeric substance.(first and second polymkeric substance can also be referred to as first and second polymkeric substance " component ".) first reactor can be designed to polymerization first polymkeric substance in solution.Will be from all or part of then second reactor that is incorporated into of the reactor effluent of first reactor, this second reactor is designed to polymerization second polymkeric substance.This configuration has guaranteed that second polymkeric substance for preparing prepares in the presence of first polymkeric substance in second reactor, this first polymkeric substance prepares in first reactor.Certainly, should be realized that, because the polymeric reagent comprises monomer and first polymkeric substance that is completed in second reactor, so can not only comprise second polymkeric substance from the polymerisate of second reactor (or in second reactor) (it be or comprise " reactor blend compositions "), and comprise one or more polymer materials, these one or more polymer materials comprise or have introduced " first polymkeric substance " or " second polymkeric substance ", but do not fall into " first polymkeric substance " or " second polymkeric substance " classification according to any definition of this paper purely.Yet, it is to be noted, should " second polymkeric substance " but can use any in many generally acknowledged analytical procedures and the technology to identify independently, directly measure or calculate no matter be.
Generally, unless otherwise prescribed, the polymerization in each reactor can be undertaken by any polymerization procedure known in the art, comprises optionally or desiredly according to circumstances regulates with employed equipment.Yet, preferably, be aggregated in reagent and product and be dissolved in fully under the condition in the solution and carry out.These polymerizing conditions can make all components of polymeric blends remain in the solution by the common solvent of two kinds of polymeric constituents that use capacity at the reaction conditions (comprising temperature and pressure) that is fit to down as polymerisation medium.
CFSTR。A kind of particularly preferred configuration is at least two Continuous Flow stirred-tank reactors (CFSTR) equipment group that is connected in series.The physical structure of this configuration and structure itself can be conventional.Yet each reactor should be able to independent feeding monomer, solvent, catalyzer etc.In addition, for the qualified stirring that provides as CFSTR should be enough strong, to avoid in reactor, the occurring unmixed zone.This design of CSFTR considers it is known in those skilled in the art.It is desirable to, removed the polar compound of catalyzer poison effect.All solvents and monomer feed can be used molecular sieve, bed of aluminium oxide or other absorption agent purifying known in the art.In preferred embodiments, in polymerization process from each reactor heat extraction.Heat extraction can be finished by means commonly known in the art, for example the various combinations of refrigeration, charging pre-cooled (adiabatic reactor), spiral coil cooling tube or these technology automatically.Adiabatic reactor with pre-cooled charging is preferred.
Polymerization temperature.Here a preferred feature that forms the method for reactor blend is the differing temps of carrying out differential responses (polymerization).Temperature can adopt equipment well known by persons skilled in the art and program, measures with one or several temp probe one or several position in reactor.In some embodiment as herein described, second polymerization temperature (for example temperature in second reactor) is higher than first polymerization temperature (for example temperature in first reactor).These temperature are stipulated hereinbefore, as the part of specific embodiments.
Reaction pressure.Pressure in each reactor should be enough under the temperature of reactor of selecting reactor content be remained in the solution.Preferably, with first polymerization (for example polymerization of in first reactor, carrying out) and second polymerization (for example polymerization of in second reactor, carrying out) " maintenance " in specified level or scope, mean that polymerization pressure keeps fully constant in the production process of at least a specific first polymkeric substance and/or reactor blend, but it should be understood that, in the successive polymerization cycle, can periodic adjustment, for example in starting, change of rank or maintenance period.Though can adopt other pressure or pressure range in some cases, preferably, first is aggregated under 2100kPa or 1750kPa or 1400kPa or 1050kPa or 700kPa any and is limited to 14,700kPa or 13,300kPa or 12,600kPa or 11,900kPa or 11 carries out under the pressure of any upper limit of 200kPa.Preferably, second polymerization (in certain embodiments, be set under the level identical with first polymerization, or in identical specialized range) under 2100kPa or 1750kPa or 1400kPa or 1050kPa or 700kPa any, be limited to 14,700kPa or 13,300kPa or 12,600kPa or 11,900kPa or 11 carries out under the pressure of any upper limit of 200kPa.
The residence time.Term as used herein " residence time " is meant the mean time that reagent that specific aggregation is used exists in particular reactor with catalyzer.This is by calculating reactor volume divided by total volumetric flow rate.The residence time in each reactor is depended on many factors, comprises the size of reactor.The example of the residence time of each reactor is 1-180 minute; Or narrower, 5-30 minute.Though can adopt other residence time or residence time scope in some cases, but preferably, first residence time was lower limit 4 minutes or arrived the upper limit 100 minutes or 90 minutes or 80 minutes or 70 minutes or 60 minutes or 50 minutes in 5 minutes or 6 minutes or 7 minutes or 8 minutes or 9 minutes.Preferably, second residence time was lower limit 4 minutes or arrived the upper limit 30 minutes or 25 minutes or 20 minutes or 15 minutes or 12 minutes or 10 minutes in 5 minutes or 6 minutes or 7 minutes or 8 minutes or 9 minutes.
Monomer.The monomer that uses in two kinds of polymerizations is set forth in other place of this paper, and determines according to the required composition of the particular polymers that will form.Monomer for example can comprise ethene (C 2) and alpha-olefin, comprise high alpha-olefin (C 4-C 20) and polyene hydrocarbon, for example non-conjugated diene class.A kind of especially effectively alpha-olefin is a propylene, but can use other high alpha-olefin as described in other place of this paper.
Solvent.As mentioned above, preferable methods comprises solution polymerization, and this needs solvent.Can use the example of the solvent of (for example being incorporated in first and second reactors) in first and second polymerizations as herein described is hydro carbons, for example aliphatic, alicyclic and aromatic hydrocarbons.Preferred solvent is C 12Or even lower level straight or branched saturated hydrocarbons, and C 5-C 9Saturated alicyclic or aromatic hydrocarbons.The example of this solvent is a hexane, butane, pentane, heptane, pentamethylene, hexanaphthene, suberane, methylcyclopentane, methylcyclohexane, octane-iso, benzene, toluene and dimethylbenzene.Hexane is preferred.Preferably, in two kinds of polymerizations, for example in two reactors, use identical solvent, and as described below solvent is carried out recirculation.
Flow out materials flow.Described as other place of this paper, in the operating process of continuation method, each reactor carries out polymerization, has produced the outflow materials flow.This flows out polymkeric substance that materials flow can produce by polymerization and catalyzer and any unreacted monomer forms.Each feature that flows out materials flow can be to have the specific aggregation substrate concentration.For example, the polymer concentration in each reactor effluent can remain in the scope of 1-30wt% or 3-20wt%, is benchmark in the gross weight of specific effluent.As what given an example in the following examples that comprise the tandem reactor configuration, the polymer concentration of first effluent is preferably only represented first polymkeric substance (this for example can measure by formed polymkeric substance is separated with non-polymer material).On the contrary, the polymer concentration of second effluent is illustrated under the given time, for example after the specific residence time or some other setting-up time points measure be present in all polymer materialss in second reactor.This polymer materials comprises described reactor blend at least, this reactor blend can comprise a certain amount of first polymkeric substance and at least a other polymkeric substance, for example belongs to second polymkeric substance of the reaction product of the reaction product of first polymkeric substance and other reagent of existing in second polymerization process or for example monomeric reaction product of other reagent itself or these two kinds of forms.Though can use other polymer concentration or concentration range in some cases, but preferably, the first effluent polymer concentration scope is any any upper limit that is limited to down among 30wt% or 25wt% or 20wt% or 16wt% or 12wt% or the 8wt% among 1wt% or 2wt% or 3wt% or 4wt% or 5wt% or the 6wt%.Preferably, the second effluent polymer concentration scope is any any upper limit that is limited to down among 30wt% or 25wt% or 20wt% or 18wt% or 16wt% or the 14wt% among 3wt% or 4wt% or 5wt% or 6wt% or 7wt% or the 8wt%.
Polymer recovery.Can be by recovery polymkeric substance with other component separating of polymkeric substance and effluent and from any effluent (for example effluent of the effluent of first reactor or second reactor).Can use conventional separate mode.For example, can by with non-solvent for example Virahol, acetone or propyl carbinol condense and from effluent, reclaim polymkeric substance, perhaps can be by with heat or steam stripped solvent or other medium pinching compound back and forth.Can with one or more conventional additives for example antioxidant in recovery process, be incorporated in the polymkeric substance.Possible antioxidant comprises Phenyl beta naphthylamine; Di-tert-butyl hydroquinone, triphenylphosphate, heptyl diphenylamine, 2,2 '-methylene radical-two (4-methyl-6-tert butyl) phenol and 2,2,4-trimethylammonium-6-phenyl-1,2-dihydroquinoline.Can consider that also other recovery method is for example by using lower critical solvent temperature (LCST), devolatilization subsequently.In series connection and configuration in parallel, when reactor effluent was merged, catalyzer may be passivated.Passivation should be used for reducing or eliminate the polymerization further out of control in the polymer recovery processes downstream.Passivation can by with the polar material that is fit to for example water mix and carry out, its residual effect after recirculation can be offset with the molecular sieve or the removing system that are fit to.
Rate of polymerization.For using the charging cooling as the adiabatic reactor that removes by the use of thermal means, total polymerization speed decides by the temperature of second reactor and the difference between the feeding temperature.Because the restriction of the availability of the commercial refrigeration plant that refrigeration is subjected to charging can be cooled to approximately-40 ℃, thus with can move second reactor and generation have expected performance for example the top temperature of the polymkeric substance of molecular weight and long chain branching improve economic benefits.Therefore, wish that second reactor moves under than the obviously higher temperature of first reactor.The other factors that influences rate of polymerization (also being called throughput rate) is that type of solvent and ratio, monomer type and polymkeric substance are formed, because heat of polymerization changes with monomeric selection.
Molecular weight.According to the desired properties of reactor blend, in some cases can conditioned reaction device blend and independent first polymkeric substance and the molecular weight characteristics (for example Mw, Mn etc.) of second polymkeric substance (polymeric constituent).This paper has described these molecular weight characteristics in other place.For example, the molecular weight characteristics of each polymkeric substance can by selective reaction actuator temperature, monomer concentration and by optional add chain-transfer agent for example hydrogen decide.Also have, molecular weight generally can reduce by improving temperature of reaction, and improves by increasing monomer concentration.
G. and linked method
The another kind of form of multistage polymeric is and linked method (polymerization in parallel).And an example of linked method in, two reactors dispose so that monomer, catalyzer and solvent independently are fed into each reactor.Note, term " first " and " second " do not hint any certain order or order, but this term uses for convenience, make word mentioned in this article " first " (polymkeric substance, polymerization, catalyzer, reactor etc.) can be equally applicable to series connection and and linked method, unless otherwise prescribed.In fact, first and second polymerizations are preferably also being carried out in the linked method simultaneously.First polymeric input thing (charging) (preferably carrying out in first reactor) can for example comprise monomer (one or both in propylene and ethene and the 'alpha '-olefin monomers), catalyst mixture and solvent with above identical in the charging described in first polymerization of series connection method.Output or effluent (for example polymerisate) also are similar to the first polymeric effluent in the series connection method, for example first polymkeric substance, catalyzer, solvent and unreacted monomer, for example propylene monomer.Preferably, first and second polymerizations all use propylene and ethene as monomer, but the ratio difference.
Second polymeric is imported thing (charging) (preferably carrying out) with above identical in the charging described in second polymerization of series connection method in second reactor, but has at least one marked difference, is exactly that charging does not comprise any first polymkeric substance.Another difference is preferably diene to be joined second polymeric area, for example in the reactor.The second polymeric charging for example can comprise monomer (ethene and alpha-olefin), catalyst mixture and solvent.Output or effluent (for example polymerisate) are second polymkeric substance, catalyzer, solvent and unreacted monomer, for example vinyl monomer.
For specific device design, device productivity can be subjected to the restriction of the bottleneck that recirculation system provides.For example, for the polymkeric substance of isodose and same polymerization ratio of division, the parallel reactor operation need be operated the more substantial solvent of recirculation than tandem reactor usually.Also have, the parallel reactor operation allows the wideer residence time and the variation of reactor condition than the tandem reactor operation.In the tandem reactor operation, by added solvent is joined in second reactor, reach the capacity limit of solvent recycled, the residence time in second reactor can be lower than the residence time in first reactor.Use parallel reactor, can independently select the residence time of each reactor, as long as the total solvent flow is no more than the recirculation capacity.
Use different polymerization temperatures also to be and a key character of linked method, more than be suitable for parallel system equally about the argumentation of tandem reactor.Also have, more than be applicable to and linked method with the same manner about the argumentation of the reaction pressure in the tandem reactor method, used.In addition, all of the residence time of tandem reactor are discussed and also are applicable to parallel reactor.
Flow out materials flow.Described as other place of this paper, in the operating process of continuation method, each reactor carries out polymerization, has produced the outflow materials flow.This flows out polymkeric substance that materials flow can produce by polymerization and catalyzer and any unreacted monomer forms.Each feature that flows out materials flow can be to have the specific aggregation substrate concentration.For example, the polymer concentration in each reactor effluent can remain in the scope of 1-30wt% or 3-20wt%, is benchmark in the gross weight of specific effluent.In parallel reactor, can there be three kinds to flow out materials flow, that is, each reactor has a kind of, also has the outflow materials flow that merges.The polymer concentration of the effluent of each of two reactors is preferably represented the polymkeric substance (this for example can measure by formed polymkeric substance is separated with non-polymer material) that only prepares in this reactor.The polymer concentration of the effluent that merges is illustrated under the given time, for example after the specific residence time or some other setting-up time points mensuration be present in all polymer materialss in these two reactors.This polymer materials comprises described reactor blend at least, this reactor blend can comprise a certain amount of first polymkeric substance and at least a other polymkeric substance, the for example monomeric reaction product of for example second polymkeric substance, or other reagent itself, or the reaction product of two kinds of forms.Though can use other polymer concentration or concentration range in some cases, but preferably, the first effluent polymer concentration scope is that lower limit 1wt% or 2wt% or 3wt% or 4wt% or 5wt% or 6wt% are to upper limit 30wt% or 25wt% or 20wt% or 16wt% or 12wt% or 8wt%.Preferably, merging effluent polymer concentration scope is that lower limit 3wt% or 4wt% or 5wt% or 6wt% or 7wt% or 8wt% are to upper limit 30wt% or 25wt% or 20wt% or 18wt% or 16wt% or 14wt%.
Polymer recovery.Can be by with other component separating of polymkeric substance and effluent and from the effluent of any one reactor or merge the effluent and reclaim polymkeric substance.Can use conventional separate mode.For example, can by with non-solvent for example Virahol, acetone or propyl carbinol condense and from effluent, reclaim polymkeric substance, perhaps can be by with heat or steam stripped solvent or other medium pinching compound back and forth.One or more conventional additives for example antioxidant can be incorporated in the polymkeric substance in recovery process.Possible antioxidant comprises Phenyl beta naphthylamine; Di-tert-butyl hydroquinone, triphenylphosphate, heptyl diphenylamine, 2,2 '-methylene radical-two (4-methyl-6-tert butyl) phenol and 2,2,4-trimethylammonium-6-phenyl-1,2-dihydroquinoline.Can consider that also other recovery method is for example by using LCST, devolatilization subsequently.
Rate of polymerization.For using the charging cooling as the adiabatic reactor that removes by the use of thermal means, the total polymerization speed of parallel reactor decides by the temperature of each reactor and the difference between the feeding temperature.Because the restriction of the availability of the commercial refrigeration plant that refrigeration is subjected to charging can be cooled to approximately-40 ℃, thus with can move these two reactors and generation have expected performance for example the top temperature of the polymkeric substance of molecular weight and long chain branching improve economic benefits.(other factors that also is called throughput rate is that type of solvent and ratio, monomer type and polymkeric substance are formed, because heat of polymerization changes with monomeric selection to influence rate of polymerization.
Molecular weight.According to the desired properties of reactor blend, in some cases can conditioned reaction device blend and independent first polymkeric substance and the molecular weight characteristics (for example Mw, Mn etc.) of second polymkeric substance (polymeric constituent).This paper has described these molecular weight characteristics in other place.For example, the molecular weight characteristics of each polymkeric substance can by selective reaction actuator temperature, monomer concentration and by optional add chain-transfer agent for example hydrogen decide.Also have, molecular weight generally can reduce by improving temperature of reaction, and improves by increasing monomer concentration.
H. Zu He series connection/parallel connection configuration
In a particularly advantageous embodiment, provide to comprise tandem reactor configuration and parallel reactor configuration, and a kind of configuration or another kind of configuration can be disposed according to the reactor assembly that some standard is selected.For example a kind of method relates to be used series connection method to prepare to have first group of performance and/or have corresponding first polymkeric substance and the reactor blend compositions of second polymer ratio (for example set polymerization ratio of division), uses subsequently and linked method prepares and has second group of performance and/or have corresponding first polymkeric substance and the reactor blend compositions of second polymer ratio (for example set polymerization ratio of division).Preferred but unnecessary is, the last reactor blend compositions that for example has first group of performance is carrying out and linked method was discharged from system before producing back one reactor blend compositions.
In certain embodiments, reactor blend compositions uses series connection method to form as mentioned above, for example be included in the charging polymerization that in solvent, makes first monomer system in first polymeric area and first catalyst system of degree of isotacticity can be provided for the unitary sequence of propylene derived, so that the mixture of first polymkeric substance and unreacted monomer to be provided, described first polymkeric substance is a propene polymer, have 〉=60wt% is by the unit of propylene derived, and comprise the sequence of the propylene derived that isotaxy is arranged and further have the melting heat that is lower than 45J/g or be lower than 105 ℃ fusing point or possess the mooney viscosity (ML (1+4)) of these two kinds of attributes and 1-45 simultaneously; And the merging charging polymerization that in second polymeric area, in solvent, makes first polymeric blends, second monomer system and second catalyst system, comprise first polymkeric substance and second mixture of polymers to provide, described second polymkeric substance is the unitary random copolymers of ethene and propylene derived, and wherein this second polymkeric substance is amorphous or has ethylene type degree of crystallinity; Wherein: this total composition has total mooney viscosity (ML (@125 ℃ of 1+4)) and be lower than the melting heat of 50J/g of 25-180.
Then, according to preassigned, described method can change into and linked method (preferably after the reactor blend compositions of removing series process production in container), and also linked method can be included in the charging polymerization that makes first monomer system in first polymeric area and first catalyst system of degree of isotacticity can be provided for the unitary sequence of propylene derived in solvent, so that the mixture of first polymkeric substance and unreacted monomer to be provided, described first polymkeric substance is a propene polymer, have 〉=60wt% is by the unit of propylene derived, and comprise the sequence of the propylene derived that isotaxy is arranged and further have the melting heat that is lower than 45J/g or be lower than 105 ℃ fusing point or possess the mooney viscosity (ML (1+4)) of these two kinds of attributes and 1-45 simultaneously; In second polymeric area, in solvent, make the merging charging polymerization of second monomer system and second catalyst system, comprise second mixture of polymers to provide, described second polymkeric substance is the unitary random copolymers of ethene and propylene derived, and wherein this second polymkeric substance is amorphous or has ethylene type degree of crystallinity; And in the presence of solvent, first polymkeric substance and second polymkeric substance are merged, wherein the binding substances of first polymkeric substance and second polymkeric substance has the mooney viscosity (ML (@125 ℃ of 1+4)) and be lower than the melting heat of 50J/g of 25-180.
Fig. 1 shows an example of the schema of staged reactor configuration.This schema is that some method as herein described when observing (especially when combine with aforesaid method) will be described, comprises relating between tandem reactor flow process and parallel reactor flow process alternately and the method for variable recirculation.Each square frame in this schema (below indicate) indication device or equipment, they can be conventional, do not need to describe in detail.Each bar line (following) expression materials flow or flow direction of material of connecting square frame should be appreciated that materials flow can be by various types of conduits pipeline for example, and these conduits can have the intermediate equipment (not shown), for example but be not limited to modular connection, valve and pump.The content that relates to the WO2002/34795 of reactor and other assembly is incorporated herein for reference, especially with also be present in this paper Fig. 1 in the assembly separator details relevant for example with reactor.
At least some embodiments for other local described method of this paper show total system 10, and it is or comprises and promptly can carry out the first polymeric structure by square frame 12, and preferably other place of this paper described " first reactor ".Square frame 14 is or comprises and can carry out the second polymeric structure, and preferably " second reactor ".Square frame 16 be can comprise be used for receiving structure 12 and 14 one or two output (for example flowing out materials flow 36 and/or 38) container and can comprise the structure of liquid-liquid phase separation equipment.Square frame 18 comprises the structure that devolatilization can take place, for example " devolatilizer ".Square frame 20 is to receive and the structure of discharging monomer and solvent, and be used for together or fractionator or some other devices of separating monomer and solvent separately optional comprising.
Polymerization among Fig. 1 can be used as series connection method (being sequential polymerization) or conduct and linked method (for example parallel polymerization) and implements.Referring to Fig. 1, first catalyzer can be incorporated into first polymeric area 12 (for example reactor) via materials flow 23, a common part as other local described catalyst mixture of this paper.Monomer can be incorporated into polymeric area 12 via materials flow 26.Fresh monomer can be introduced via materials flow 28.First polymkeric substance (for example propene polymer) is produced in polymeric area 12.When adopting configured in series, propylene effluent (comprising propene polymer) is incorporated into second polymeric area 14 via materials flow 34, wherein carries out second polymerization to produce second polymkeric substance (for example ethene polymers).To leave the second polymeric effluent (comprising propene polymer and ethene polymers) via materials flow 36 is incorporated in first separator 16, carry out separating treatment therein, liquid-liquid phase separation for example, thereby the component and the non-polymeric ingredients (that is, not having polymkeric substance basically) that will be rich in polymkeric substance are separated.This non-polymeric ingredients comprises solvent, unreacted monomer and catalyzer.The component that is rich in polymkeric substance preferably mainly comprise polymer composition as herein described, and this polymer composition can be described to contain propene polymer and polyvinyl reactor blend.Yet this component that is rich in polymkeric substance also comprises the material such as unreacted monomer (for example propylene, ethene and diene) and so on that does not successfully remove in liquid liquid separator.Therefore, this component that is rich in polymkeric substance is fed into second separator via materials flow 40, and for example devolatilizer 18, and it discharges vapor stream 48 and liquid stream 46, and this liquid stream 46 has the polymkeric substance of greater concn than the materials flow 40 before the devolatilization.Materials flow 40 can further suitably be processed, to reclaim solvent-free product.The vapor stream 48 that will comprise unreacted monomer and solvent is incorporated into structure 20, and monomer and solvent can discharge thus via materials flow 52, perhaps are incorporated in the recycle stream 44 via materials flow 50 again.Structure 20 can comprise one or more fractionator (not shown), can separately or unite whereby to remove the volatilization monomer, for example ethene, propylene and/or diene (as ENB).Structure 20 can also comprise the condenser that the steam content of materials flow 48 is converted into liquid.Liquid output materials flow 50 can comprise monomer and solvent in some cases, materials flow 50 can be incorporated in this liquid recycle stream 42, the composition of liquid recycle stream 42 optionally can be regulated according to introducing monomeric what or amount again, so that recycle stream 44 to be provided.Recycle stream 44 can be fed into polymeric area 14 again via materials flow 30, and can for example ethene or diene join in this input materials flow 30 with additional monomer.Recycle stream 46 can be fed into polymeric area 12 again via materials flow 26, and can for example propylene or ethene join in this input materials flow 26 with additional monomer via materials flow 28.
As mentioned above, the method among Fig. 1 can be used as parallel polymerization enforcement.In addition, the configuration among Fig. 1 can allow (above-mentioned) series connection method and below change or switch between the parallel polymerization that will discuss.Use the parallel polymerization method, leave the outflow materials flow 34 of first polymeric area 12 and preferably walk around second polymeric area 14 via bypass materials flow 38.Simultaneously, monomer is fed into second polymeric area 14 via input materials flow 30, and this input materials flow 30 can comprise from the fresh monomer of materials flow 32 and/or as the monomer of the part of recycle stream 44 interpolation.According to the parallel connection configuration, first polymkeric substance (propene polymer) is not incorporated into second polymeric area 14, but only adds monomer, solvent and catalyzer via materials flow 30 and 24.Second (ethene) polymkeric substance forms in second polymeric area, the effluent that comprises ethene polymers, unreacted monomer, solvent and catalyzer leaves second polymeric area via materials flow 36, and with from the effluent that comprises first (propylene) polymkeric substance of first polymeric area enter this container (as shown in Figure 1) entering this container before or alternatively after (not shown) merge.As mentioned above, the effluent of merging comprises the polymer composition that contains propene polymer (forming) and ethene polymers (forming) in first polymeric area in second polymeric area.Some embodiment relates to the method for using same reactor to prepare different elastic compositions, and for example, wherein propene polymer is different with polyvinyl ratio, or wherein propene polymer is different with polyvinyl the composition separately.The ratio of the polymkeric substance of producing in each reactor can change.In one aspect of the invention, provide a kind of be used for series connection method configuration change (conversion) for and linked method configuration and/or will and the linked method configuration change (conversion) for the device that series connection method disposes disposes, preferably provide according to preassigned.Preferably, to small part according to following observed value one or more (with preferred all) (they can change or conversion before measure (measuring in advance)) select and linked method: (a) preselected polymerization ratio of division (total weight that adds second polymkeric substance by the weight of first polymkeric substance divided by first polymkeric substance); (b) propylene content of propene polymer (for example first polymkeric substance); (c) ethylene content of reactor blend compositions (merging of first and second polymkeric substance).Especially preferred embodiment comprises with series connection method and forms first elastic composition, the flow direction that changes monomer and solvent then to and linked method so that the method for second elastic composition with different polymerization ratio of division or different monomers (C3 or C2) content to be provided.Preferably, when the polymerization ratio of division is more than or equal to preselected " C3C2 coefficient ", adopt and linked method.In a broad sense, the C3C2 coefficient is defined as for example depending on any value of FPP (the first polymkeric substance propylene content) or BPE (blend polymkeric substance ethylene content) or some the calculating summations of the two.Preferred C3C2 coefficient is defined as 575* (100-FPP) more accurately 0.14* (BPE) -0.81(equation 1).Preferably, this series connection method is being changed into when the polymerization ratio of division is equal to or greater than the C3C2 coefficient and linked method.The accurate timing that changes may need not to be strict demand, just takes place in the change of polymerization ratio of division or when the target polymerization ratio of division that suggestion changes is determined usually.Following table 1 shows and different FPP and the related different maximum polymerization ratio of division of BPE value, makes should implement and linked method (but not series connection method) when any polymerization ratio of division of maximum polymerization ratio of division shown in being equal to or greater than (for example, the setting point of suggestion).
Table 1
Setting point Maximum polymerization ratio of division FPP(wt％C3) BPE(wt％C2)
1 46 95 24
2 36 95 40
3 22 95 64
4 48 88 27
5 38 88 42
6 23 88 64
7 50 80 30
8 40 80 44
9 25 80 65
Can produce the blend of the following scope in the table 2 according to method as herein described:
Table 2
First polymkeric substance (wt%C2) Second polymkeric substance (wt%C2) Polymerization ratio of division scope Serial or parallel connection
8-16 40-80 ＜20 to＜60 Series connection
8-16 40-80 ＞20 to＞60 In parallel
I. recirculation
A particularly advantageous characteristics of some method as herein described is variable recycling feature, and this recycling feature has been imagined several different modification (embodiment).In at least one modification of this method, will be both quantitative non-polymer from effluent (for example first effluent, second effluent or merge effluent) is incorporated among any one or two of first and second polymeric areas, and this first and second polymeric area is being represented with first and second reactors in some embodiment at least.Preferably, the amount that is incorporated into the non-polymer in first and second polymeric areas differs from one another separately.The character that depends on first and second polymkeric substance, this recycled materials can be solvent, catalyzer or monomers alone or in combination.
Therefore, in a preferred embodiment, prepare the elastic composition that comprises (above-mentioned) first polymkeric substance and second polymkeric substance with continuation method.This method preferably include use identical or different catalyst system (more than be described in more detail) and also be used for each polymeric area preferably include propylene with ethene but the different monomer system of ratio, respectively in the presence of the solvent that is preferably common (identical) solvent in first and second polymeric areas (serial or parallel connection) formation first polymkeric substance and second polymkeric substance.As mentioned above, second polymerization temperature preferably is much higher than first polymerization temperature, for example high 20 ℃ or more, second monomer system that is incorporated into second polymeric area preferably includes diene, yet, preferably in first polymeric area, do not add diene or add a spot of diene (be lower than 2wt% or be lower than 5wt%).This method is included in polymerization first and second polymkeric substance in the different polymeric areas, and the reactor blend that comprises first polymkeric substance, second polymkeric substance, solvent and unreacted monomer is provided.Then, this method comprises from reactor blend except that desolvating and unreacted monomer; The recycle stream that will contain solvent and unreacted monomer is incorporated into first polymeric area and second polymeric area; And reclaim and to comprise first polymkeric substance and second polymkeric substance and to have 16-180 or the mooney viscosity of other level of other local defined of this paper (or scope) (elastic composition of ML (@125 ℃ of 1+4)).
Preferably, described method comprises recycle stream is divided into first recycle stream and second recycle stream, and this first recycle stream is incorporated into first polymeric area and this second recycle stream is incorporated into second polymeric area.Preferably, select the amount of the solvent in second recycle stream to be enough to required second polymerization temperature of (i) acquisition with respect to first polymerization temperature; Or (ii) obtain hereinafter and other local described required polymerization ratio of division of this paper.
As described in other place of this paper, from reactor blend, remove and desolvate and unreacted monomer can comprise that (i) allows reactor blend carry out first separating step, so that first part and the second lean solvent part that is rich in solvent to be provided; (ii) allow first lean solvent partly carry out second separating step, so that second part and the second lean solvent part that is rich in solvent to be provided; The part that (iii) first part and second that is rich in solvent is rich in solvent merges, so that the recycle stream of merging to be provided; (iv) the recycle stream that will merge is incorporated into first polymeric area and second polymeric area.
In addition, from described mixture, remove and desolvate and unreacted monomer can comprise and allows at least a portion of this mixture carry out liquid phase separation, so that part (normally poor polymer moieties) and the lean solvent part (normally being rich in the part of polymkeric substance) that is rich in solvent to be provided, wherein this part that is rich in solvent is introduced in first polymeric area and second polymeric area.
In addition, from described mixture, remove and desolvate and unreacted monomer can comprise and allows at least a portion of this mixture carry out devolatilization, so that part and the lean solvent part that is rich in solvent to be provided, wherein this part that is rich in solvent is introduced in first polymeric area and second polymeric area.
Some embodiment relates to uses same reactor but the different method for preparing different elastic compositions of recirculation ratio of division between the reactor.Therefore these methods can comprise the recirculation flow that is adjusted to different reactor.In a broad sense, " recirculation volume " (being applicable to intermittently and the term of continuation method) can change.In continuation method, yet it provides or establishes " recirculation rate " (unit time is incorporated into the amount in the reactor) according to some standard." recirculation rate " is a generic term, comprises that (a) unit time is fed into the total amount of the recycle stock of two reactors (" total recirculation rate ") or (b) unit time is fed into the amount (" the first reactor recirculation rate ") of the recycle stock of first reactor or (c) unit time is fed into the amount (" the second reactor recirculation rate ") of the recycle stock of second reactor.Under those situations, " recycle stock " defines according to solvent at least, but can also be that solvent adds unreacted monomer, or as total recycle stream that can also comprise catalyst recycle.In certain embodiments, can regulate any one (lbs or kg/h) of above-mentioned recirculation rate, be used for first recirculation rate is changed into different recirculation rate (for example second speed or third speed etc.) (kg/h)." recirculation ratio of division " is defined as the first reactor recirculation rate divided by total recirculation rate, can represent with (as described below) percentage.
In at least one embodiment, at least according to following observed value (they can change or conversion before measure (preliminary assay)) one or more (with all preferred) regulate the recirculation ratio of division: (a) preselected polymerization ratio of division (total weight that adds second polymkeric substance by the weight of first polymkeric substance divided by first polymkeric substance); (b) temperature of second polymeric area (for example second reactor); (c) temperature of first polymeric area (first reactor).
Especially preferred embodiment comprises uses series connection method to form first elastic composition, change is fed into and the monomer of linked method and the flow of solvent according to above-mentioned standard (being the C3C2 coefficient) then, so that second elastic composition with different polymerization ratio of division or different monomers (C3 or C2) content to be provided; Further change the recirculation ratio of division, preferably according to following standard.The preferred normal flow control valve that uses is controlled the recirculation ratio of division.
When using any above-mentioned series connection method to prepare elastic composition, " recirculation ratio of division " is defined as the percentage of the total recirculation solvent that is incorporated into first polymeric area (for example first reactor), and it should be represented with equation 2.The equation of representing with equation 2 should exist at some time points of this method, that is, in the forming process of elastic composition, more preferably, it keeps (but allowing common technological fluctuation (being higher or lower than this amount) in continuation method) in entire method.In equation 2, PS=polymerization ratio of division; RT2=second temperature of reactor (℃); And RT1=first temperature of reactor (℃).Equation 2 regulations, the recycle stream percentage of reactor 1 equals 2.8* (PS) 0.67* (RT2/RT1) 1.11
When preparing elastic composition with any above-mentioned and linked method, " recirculation ratio of division " is defined as the percentage of the total recirculation solvent that is incorporated into first polymeric area (for example first reactor), and it should be represented with equation 3.The same with equation 2, the equation of representing with equation 3 should exist at some time points of this method, and preferably maintenance in entire method (allowing fluctuation).In equation 3, PS=polymerization ratio of division; RT2=second temperature of reactor (℃); And RT1=first temperature of reactor (℃).Equation 3 regulations, the recycle stream percentage of reactor 1 equals 4.5* (PS) 0.55* (RT2/RT1) 0.67
For the tandem reactor configuration, following table 3 shows and different PS values (polymerization ratio of division) and the related different recirculation ratio of division of RT2/RT1 value.For the parallel reactor configuration, following table 4 shows and different PS values and the related different recirculation ratio of division of RT2/RT1 value.Reflected some embodiment at least, each combination is confirmed as a set(ting)value.
Table 3
Set(ting)value Recirculation ratio of division (%) The polymerization ratio of division RT2/RT1
1 44 10 3.0
2 61 10 4.0
3 78 10 5.0
4 28 10 2.0
5 39 10 2.7
6 50 10 3.3
7 21 10 1.5
8 28 10 2.0
9 36 10 2.5
10 83 50 2.0
11 60 50 1.5
12 83 50 2.0
13 93 30 3.0
14 71 20 3.0
15 82 25 3.0
16 97 20 4.0
17 93 13 5.0
Table 4
Set(ting)value Recirculation ratio of division (%) The polymerization ratio of division RT2/RT1
1 33 10 3.0
2 40 10 4.0
3 47 10 5.0
Set(ting)value Recirculation ratio of division (%) The polymerization ratio of division RT2/RT1
4 25 10 2.0
5 31 10 2.7
6 36 10 3.3
7 21 10 1.5
8 25 10 2.0
9 30 10 2.5
10 62 50 2.0
11 51 50 1.5
12 62 50 2.0
13 61 30 3.0
14 49 20 3.0
15 55 25 3.0
16 59 20 4.0
17 54 13 5.0
J. polymerizing catalyst
By wide region, described composition can use any SSC (single-site catalysts) preparation.This catalyzer can be to contain periodictable 3-10 group 4 transition metal and at least a transition metal complex that keeps being bonded to the assistant ligand of transition metal in polymerization process usually.Preferably, this transition metal uses with the reduction cation state, and stablizes with promotor or activator.
Described assistant ligand can be the structure that can form the π key, for example cyclopentadiene base class ring structure.This assistant ligand can also be pyridine or amino ligands.This transition metal is the 4th family's element of periodictable preferably, for example titanium, hafnium or zirconium, they in polymerization with d 0The univalent cation attitude is used, and has the assistant ligand that one or two is hereinafter described in detail.The key character that is used for this catalyzer of polycoordination is the part that can capture and the part that can insert ethene (olefinic) group.
Described transition metal complex can apply to a certain degree spatial order to propylene monomer with suitable chirality.More under the situation of high-molecular weight first polymkeric substance or higher polymerization temperature, preferred non-coordination or weakly coordinating anion (the non-coordination anion of term as used herein comprises weakly coordinating anion) are as promotor at needs.Alternatively, can use aikyiaiurnirsoxan beta or the title complex of having introduced oxygen-constructed of aluminium part.
The precursor of non-coordination anion can be used with the transition metal complex of supplying with the reduction valence state.This precursor can carry out redox reaction.This precursor can be a neutral, borane complexes for example, and can form transition-metal cation by capturing part from this precursor.This precursor can be for example borate ion pair that is neutralized and/or eliminates in some mode of precursor cation.This precursor cation can be as at the ammonium salt described in EP 277 003 and the EP277 004.This precursor cation can be as at the triphenylcarbenium derivative described in the EP 426 637.Non-coordination anion can be a 10-14 family title complex, and wherein boron or aluminium are can be by halogenation, the charged atom of fluorizated part shielding especially.The 10-14 family non-carbon type negatively charged ion that preferred four aryl replace, those of the hydrogen atom on the hydrogen atom on the especially fluorine-based substituted aryl or the alkyl substituent of these aryl.
Described non-coordination anion can be with respect to about equimolar amount of transition metal complex, for example at least 0.25, preferred 0.5, especially 0.8 and 4, preferred 2 and especially 1.5 the amount of for example being no more than use.
Described transition metal complex can be the pyridine amine complex that is used for olefinic polymerization, for example those described in the WO 03/040201.This transition metal complex can be to carry out the periodicity intramolecular rearrangement, so as to provide that required tacticity interrupts follow the change title complex, for example at Waymouth, US patent No.6, those described in 559,262.This transition metal complex can be as described in the Rieger EP1 070 087 propylene being inserted the upright structure rigidity title complex with mixed influence.
Preferably, described transition metal complex is the chirality bridging dicyclopentadiene radical derivative with following general formula:
L AL BL C iMDE
L wherein AAnd L BBe to be connected in the replacement of M or unsubstituted cyclopentadienyl or heterocyclic pentylene Kiev with the π key to help part, L wherein AAnd L BPart connects base with the covalent linkage bridging together, L by the 14th family's element C iBe to have with dative bond to be connected in the optional neutral of M, non-oxide part (i equals 0-3); M is the 4th or 5 group 4 transition metals; D and E are the unstable part of single anion independently, are connected in M with the σ key separately, optional mutual bridging or and L AOr L BBridging.Single anion ligand is replaceable by the activator that is fit to, and inserts to allow polymerisable monomer or macromonomer, so that carry out polycoordination on the empty hapto of transition metal component.
When using catalyzer, the total catalyst system generally comprises one or more organometallic compounds as scavenging agent in addition.Be intended to comprise those compounds of effectively from reaction environment, removing polar impurity and improving catalyst activity as this compounds that uses in this application.
In at least one embodiment, polymerization process is made up of following steps or is may further comprise the steps: polymerization in the presence of the catalyzer that comprises two (cyclopentadienyl) metallic compounds and (1) non-coordination compatible anionic activator or (2) alumoxane activator.The limiting examples of operable catalyst system is at US patent Nos.5, states in 198,401 and 5,391,629, and its disclosure is incorporated herein for reference thus.In a particular aspects of this embodiment, alumoxane activator can be used to the amount of 20,000: 1 aluminium and metallocenes mol ratio to provide 1: 1.In another particular aspects of this embodiment, non-coordination compatible anionic activator can use with the amount of mol ratio that 10: 1 to 1: 1 bicyclic pentadiene metallic compound and non-coordination anion are provided.In another particular aspects of this embodiment, this polyreaction comprises the time that allows monomer react 1 second to 10 hours under-0 ℃ to 200 ℃ temperature in the presence of catalyst system as herein described.
In certain embodiments, first polymkeric substance of the present invention can prepare in the presence of chiral metallocene catalyst and activator and optional scavenging agent.The preferred homogeneity of using single central metal cyclopentadienyl catalyst to improve polymkeric substance.Because only need limited tacticity, so can use many multi-form single-site catalysts.Possible single-site catalysts is a metallocenes, for example at US patent No.5,026, described in 798 those, they have single cyclopentadienyl rings, advantageously have been substituted and/or have formed the part of polynuclear plane, and heteroatoms (common nitrogen-atoms, but also may be phosphorus atom or phenoxy group) be connected in the 4th group 4 transition metal, preferred titanium, but may be zirconium or hafnium.Another example is with B (CF) 3Activatory Me 5CpTiMe 3, be used to prepare the elastomeric polypropylene that has at the most 400 ten thousand Mn.Referring to Sassmannshausen, Bochmann, Rosch, Lilge, J.Organomer.Chem. (1997) 548,23-28.
Other possible single-site catalysts be belong to have magnesium-yttrium-transition metal, the metallocenes of the dicyclopentadiene radical derivative of preferred hafnium or zirconium.This metallocenes can be non-bridged, as US patent No.4, and 522,982 or US patent No.5, described in 747,621.This metallocenes can be suitable for preparing the unitary polymkeric substance that mainly comprises propylene derived, as US patent No.5, and 969,070, this patent is used non-bridged dichloro two (2-phenyl indenyls) to close zirconium to prepare the homogeneous polymers that fusing point is higher than 79 ℃.This cyclopentadienyl rings can be a part that replaces and/or be polycyclic system, as described in the above US patent.
Other possible metallocenes comprises that wherein for example silicon or carbon atom connect and select group to occupy those of two residual valences two cyclopentadienyls by abutment, common monatomic abutment.This metallocenes is stated in following document: US patent No.6,048,950 (it discloses two (indenyl) two (dimetylsilyl) of dichloro and has closed zirconium) and MAO); WO98/27154 (its two indenyls that disclose the bridging of dimethylformamide dimethyl base silyl close hafnium and non-coordination anion activator); EP1 070 087 (it is catalyst based that it discloses the bridging dicyclopentadiene that has asymmetric element between two cyclopentadienyl ligands, is used to obtain the rubber-like polymkeric substance).US patent Nos.6 has also described described metallocenes in 448,358 and 6,265,212.
The activation method of single-site catalysts can change.Can use aikyiaiurnirsoxan beta and preferable methyl aikyiaiurnirsoxan beta.Use is so that for example any way described in EP277 004, the EP426 637 etc. is derived and the non-coordination or the weakly coordinating anion activator (NCA) that produce obtain high molecular at the publication document.It is generally acknowledged that activation comprises and captures for example methyl of anionic group, forming the metallocenes positively charged ion, but, can produce zwitter-ion according to some document.The NCA precursor can be the ion pair of borate or aluminate, and wherein precursor cation is eliminated when activating in some mode, for example, and trityl of four (pentafluorophenyl group) boron or ammonium derivative (referring to EP277 004).This NCA precursor can be a neutral compound, borine for example, and it forms positively charged ion (referring to EP426 638) by capturing and introducing the anionic group of capturing from metallocenes.
K. concrete catalyzer
As described in other place of this paper, in certain embodiments, the polymerization in different reactor can be carried out in the presence of identical catalyst mixture, and in other embodiments, can carry out in the presence of different catalyst mixtures.Term as used herein " catalyst mixture " (catalyst system) comprises at least a catalyzer and at least a activator, but depends on context, and " catalyzer " mentioned in this article also infers activator usually.
Suitable catalyst mixture can be transported to corresponding reactor in every way.For example, it can be used as solution or slurry is transported to reactor independently, just activates in the pipeline before reactor, and perhaps pre-activation is also delivered to reactor as activated solution or shurry pump.Be aggregated in each reactor and carry out, wherein reagent component (for example required monomer, comonomer, catalyzer/activator, scavenging agent and optional properties-correcting agent) preferably is added continuously in the suitable reactor.In certain embodiments, two kinds of catalyst mixtures are joined in first reactor, and in other embodiments, a kind of catalyst mixture is joined in first reactor, the different catalysts mixture is joined in second reactor (though in subsequent operations, can be incorporated into product mixtures in second reactor from first reactor from least some first catalyst mixtures of first reactor.
In preferred embodiments, two kinds of different catalysts are added as the part of differential responses agent charging, for example " first catalyzer " can be the part of " the first reagent charging ", " second catalyzer " can be the part of " the second reagent charging ", but at least some embodiments (for example tandem reactor), first and second catalyzer in second reactor feed simultaneously there to be (for example, when first effluent is supplied with second reactor) to a certain degree.Preferably, at least some embodiments, first catalyzer is a chiral catalyst, and second catalyzer is non-chiral catalyst.
In some embodiment of described method and composition, no matter be that series connection or first and second polymerizations in parallel can be used identical catalyst mixture separately.For example, in some method, in two kinds of polymerizations, can use US patent No.6, some catalyst mixture described in 207,756, this patent are introduced for reference thus in full, especially describe the part of catalyst mixture, for example the 8th hurdle the 20th row is to the 14th hurdle the 21st row.Preferred catalyzer be isotactic (isospecific) those.The operation that is formed with the specific examples of catalyst system provides in the embodiment 1 of this patent.
First catalyzer.First catalyzer is chiral catalyst preferably.In at least one specific embodiments, first is aggregated under the existence of first catalyzer that belongs to " single site polymerization catalyzer " and carries out, this catalyzer preferably only allows to add two kinds of different monomers sequences, for example propylene sequences and ethene sequence by single statistical.First catalyzer is thorough mixing in Continuous Flow stirring tank polymerization reactor preferably, and feasible all basically polymer chains for this polymkeric substance only provide single polymerization environment.Preferably, mean that it combines with activator in some mode with this first catalyst activation.
As at least one example, first catalyzer can comprise two (cyclopentadienyl) metallic compounds, and can combine with (1) non-coordination compatible anionic activator or (2) alumoxane activator.(all " catalyzer " of mentioning here preferably also comprise activator, unless otherwise prescribed.) limiting examples of operable catalyst system (comprising activator) is at US patent Nos.5, states in 198,401 and 5,391,629, their disclosure is incorporated herein for reference thus.In a particular aspects of this embodiment, alumoxane activator can be used to the amount of 20,000: 1 aluminium and metallocenes mol ratio to provide 1: 1.In another particular aspects of this embodiment, non-coordination compatible anionic activator can use with the amount of mol ratio that 10: 1 to 1: 1 bicyclic pentadiene metallic compound and non-coordination anion are provided.In another particular aspects of this embodiment, this polyreaction comprises the time that allows monomer react 1 second to 10 hours under-0 ℃ to 200 ℃ temperature in the presence of catalyst system as herein described.
Second catalyzer.Second catalyzer (if being different from first catalyzer) is the achirality catalyzer preferably, also preferred thorough mixing in the Continuous Flow stirred-tank reactor.Preferably, mean that it combines with activator in some mode with this second catalyst activation.The example of second catalyzer has description in other place of this paper, and in WO00/24793 description is arranged also, and this patent is introduced for reference thus.
Embodiment
Following examples have been described the method that the successive polymerization of being undertaken by the Continuous Flow stirred-tank reactor that uses two configured in series forms the reactor blend of being made up of two kinds of dissimilar polymkeric substance, to this two reactor continuous feed different monomers mixtures and catalyst mixture.Hexane solvent is fed in each reactor, so that the content of each reactor remains in the solution.The temperature of second reactor is apparently higher than first reactor.Each catalyst stream is used volume pump to be fed into the respective reaction device then and is prepared by the pre-mixing in 900ml toluene with catalyzer and activator.Catalyst mixture A (being fed into reactor 1) is the non-mixture that dimethylformamide dimethyl base silyl two (indenyl) closes hafnium catalyst and four (pentafluorophenyl group) boron xylidine activator that supports.Catalyst mixture B (being fed into reactor 2) is as at US patent No.6, the disclosed non-mixture that dimethyl two-(right-the triethylsilyl benzyl) carbyl (cyclopentadienyl) (2-7 di-t-butyl fluorenyl) closes hafnium and employed identical activator in catalyst mixture A that supports among 506,857 (catalyst A) embodiment 1 and 4.Catalyzer adds speed and provides in table 5.In reactor 1, use tri-n-octylaluminium as scavenging agent.
Table 5
Reactor Can wt.(g) The Can time (min) Catalyst mixture Catalyzer speed Scavenging agent Hydrogen (g/h) C 2 (g/h) C 3 (g/h) ENB (g/h) C 6 (g/h) T (℃)
1 534 10 A 0.00233 0.118 0 12 199.8 0 3564 47
2 2484 30 B 0.01101 0 0 228 45 32 1782 117
Table 6
Reactor Throughput rate (g/hr) Polymerization ratio of division (%) C 2Transformation efficiency (%) C 3Transformation efficiency (%) ENB transformation efficiency (%)
1 74.6 26 134 29 N/R
2 289.6 74 44 48
The effluent that comprises first polymer product has been produced in reactor 1 polymerization.This effluent that will comprise unreacted monomer and catalyst mixture is fed into reactor 2, carries out polymerization at this under the differential responses condition.For example, in reactor 2, use obviously higher temperature of reactor.Also have, introduce polyene hydrocarbon (5-ethidine-2-norbornylene).The throughput rate of each reactor is by regularly collecting effluent, and evaporating solvent and mensuration remaining solid concentration are determined subsequently.The throughput rate of reactor 1 is determined by reaction in the stopped reaction device 2 and the effluent that uses this same processes regularly to collect reactor 1 then.When two reactors fully move, use the output of reactor 2 to measure total throughput rate according to same processes.Use this information, calculate the ratio of reactor 1 throughput rate and total throughput rate.This ratio is called as " polymerization ratio of division " in table 6.Use catalyst make-up and feeding rate and throughput rate, press catalyst efficiency and calculate catalyst productivity (g polymkeric substance/g catalyzer).
The various performances of the polymer product that forms in each reactor are reported in table 7 and 8.As seen in Table 7, the polymkeric substance that forms in the reactor 1 has the ethylene content of 21wt%.On the contrary, the polymer product of discharging from reactor 2 has the 61wt% ethylene content, and this polymer product is to comprise that the polymkeric substance that forms in the reactor 1 adds the reactor blend of other polymkeric substance that forms in the reactor 2.The ethene value of second polymkeric substance that is calculated by first polymkeric substance and reactor blend ethylene content and polymerization ratio of division is 75%.The value of ENB is 6.9%.Other that reported measure performance comprise mooney viscosity, melt index, molecular weight data and branching measure (g ' and BI), all reflections in table 7 and 8.
Table 7
Reactor C 2 (％) ENB (％) ML (1+4@125℃) MI The little angle of Mw laser light scattering (Lalls) The little angle of Mz laser light scattering Mw DRI
First polymkeric substance 21 0 4.2 1697 37 2704 19 1639 66
Reactor C 2 (％) ENB (％) ML (1+4@125℃) MI The little angle of Mw laser light scattering (Lalls) The little angle of Mz laser light scattering Mw DRI
Second polymkeric substance 75 6.9
Reactor blend 61 5.1 54 2506 01 4573 61 230 310
Table 8
Reactor Mn DRI g’ BI Mw/Mn Mz/Mn
Reactor 1 83646 0.963 0.963 2.03 1.59
Reactor 1+ reactor 2 86947 0.951 0.949 2.88 1.83

Claims (12)

1. preparation contains the continuation method of the elastic composition of first polymkeric substance and second polymkeric substance, and this method comprises:
In first polymeric area, use first catalyst body to tie up to first monomer system that polymerization in the solvent comprises propylene and ethene, so that first polymkeric substance to be provided, this first polymkeric substance has 60wt% or more by the unit of propylene derived, comprises the sequence of the propylene derived that isotaxy is arranged and further has the melting heat that is lower than 45J/g or be lower than 105 ℃ fusing point or possess the mooney viscosity of these two kinds of attributes and 1-45 simultaneously; Wherein melting heat or fusing point use the ASTME-794-95 program determination by dsc, and (measure down for @125 ℃ by 1+4) at ML for mooney viscosity;
In second polymeric area, use second catalyst body to tie up to second monomer system that polymerization in the solvent comprises ethene, so that second polymkeric substance to be provided, this second polymkeric substance is an elastomerics and amorphous or have the degree of crystallinity that comes from ethene;
This first polymkeric substance and second polymkeric substance are merged in the mixture that comprises solvent and unreacted monomer;
From this mixture, remove and desolvate and propylene and vinyl monomer, so that elastic composition to be provided; And
Propylene and vinyl monomer and solvent recycled are used for polymerization; Wherein:
This first polymerization proceeds to propylene monomer is depleted to and is lower than the level that is used to prepare this second polymkeric substance desired level;
This second polymerization and recirculation proceed to vinyl monomer reduced to and are lower than the level that is used to prepare this first polymkeric substance desired level, and add for first polymerization and additionally to replenish propylene monomer and to add additional make-up ethylene monomer for second polymerization.
2. method according to claim 1, wherein said elastic composition has the mooney viscosity of 16-180; Wherein melting heat or fusing point use the ASTME-794-95 program determination by dsc, and (measure down for @125 ℃ by 1+4) at ML for mooney viscosity.
3. method according to claim 1, wherein said second polymkeric substance are the random copolymerss of ethene and propylene and diene.
4. method according to claim 1, wherein in the series system operation, at least a portion of the effluent of described first polymeric area is incorporated into second polymeric area continuously, and/or in parallel way operation, with at least a portion of the effluent of described first polymeric area and the effluent merging of second polymeric area.
5. method according to claim 1, the polymer phase of producing in wherein said first polymeric area is 5-95 to the polymerization ratio of division of the total polymer produced in first and second polymeric areas.
6. method according to claim 1, comprising first polymkeric substance and second mixture of polymers by the devolatilization post-treatment of assigning to, to form pellet or packing material.
7. method according to claim 1, the mark of first polymkeric substance of wherein being produced and the mark of second polymkeric substance are independently by cutting apart from the amount that supplies to the first and second polymeric solvents of recirculation with by providing additional fresh feed to control to change flow and each polymeric heat-removal capability, this first is aggregated under the temperature of the fusing point that is lower than first polymkeric substance and carries out, and this second is aggregated in than carrying out under the temperature that is used for high 20-200 ℃ of the first polymeric temperature.
8. method according to claim 1 wherein uses transfer agent to limit molecular weight in first or second polymeric area.
9. method according to claim 1 wherein is divided into described recycle stream first recycle stream and second recycle stream, and this first recycle stream is incorporated into first polymeric area and this second recycle stream is incorporated into second polymeric area.
10. method according to claim 9 wherein selects to be enough to obtain (i) required second polymerization temperature; Or the amount of the solvent in second recycle stream of (ii) required polymerization ratio of division.
11. method according to claim 1 wherein, is removed from described mixture and is desolvated and unreacted monomer comprises that (i) allows this mixture carry out the first separated from solvent step, is used for concentrating the polymkeric substance of residual solvent; (ii) allow this concentrated solution carry out second step, be used for further except that desolvating and forming the molten polymer that granulation is used; The solvent that (iii) will extract from first and second steps merges, so that the recycle stream of merging to be provided; (iv) the recycle stream that will merge is incorporated into first polymeric area or second polymeric area or first polymeric area and second polymeric area in the two.
12. method according to claim 11, wherein the first step comprises and allows at least a portion of described mixture carry out liquid-liquid phase separation, thereby part and the lean solvent part that is rich in solvent is provided.
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