CN101048458A

CN101048458A - Elastomeric reactor blend compositions

Info

Publication number: CN101048458A
Application number: CNA2005800373241A
Authority: CN
Inventors: P·S·拉维尚卡尔
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2004-10-13
Filing date: 2005-09-28
Publication date: 2007-10-03
Anticipated expiration: 2025-09-28
Also published as: ES2370503T3; CN101048458B

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

Cross reference to related applications

This application claims 60/645,138 equity that serial number on the January 20th, 60/618,301 and 2005 proposed on October 13rd, 2004 proposes, the disclosure of this two applications is incorporated by reference.

Background

Invention field

This application involves elastomeric reactor blend compositions and it is used to prepare the continuation method of the elastic composition including first polymer and second polymer with different level of crystallization and/or type.

Description of related art

Embodiment of the present invention is related to elastomeric reactor blend compositions.People are being constantly working to the polymer composition that there is ideal performance and attribute to balance for preparation, to obtain the composition for the enhancing that can be used for many applications.Depending on expected concrete application and specific blend, this composition enhancing itself can show in numerous ways.This enhancing includes but is not limited to the processing performance of (1) in the technique of such as grinding, extrusion, calendering and injection molding etc under melt；(2) initial physical performance in the solid state, such as toughness, viscosity, bonding force, tear resistance, stretching and elongation；(3) if to solidify or vulcanize, the improvement of solidification rate and state；(4) long term physical performance such as heat ageing determined by such as being kept at high temperature by this physical property.Various methods have been proposed to obtain the polymer composition with required performance and attribute, but these methods have the shortcomings that it is many.

US patent No.6,635,715 discloses the ethylene-propylene elastomeric with low-level isotactic crystallinity containing different amounts of highly crystalline propylene based polymer.These blends are prepared by the various components of physical blending.

US patent No.6,329,477 disclose using tandem reactor in the production using the polymer composition of bicyclic pentadiene metalloid cyclopentadienyl catalyst, but the composition is free of the two kinds of polymer with dramatically different propylene content.It is related to producing other patents of polymer composition being US patent Nos.6,319,998 and 6,207,756.

WO98/02471 and US patent No.6,545,088, which is disclosed, uses tandem reactor in using monocyclopentadienyl metalloid cyclopentadienyl catalyst production EP rubber.

WO03/040201 discloses the tandem reactor operation using non-metallocene type catalyst, to produce the polymer composition with different crystallinity.There is no suggestion that using making molecular weight etc. be suitable for the recycling of industrial elastomeric application or the continuous operation method of processing conditions.

Other background technique bibliography include US patent No.6,747,114, US patent application publications 2004/198913, WO1997/36942 and WO2002/34795.

The purpose of the present invention is develop novel polymer compositions, wherein the useful elastomer of total Mooney viscosity with 16-180 is provided using the benefit of series connection and/or parallel reactor operation, and it is recycled using tandem reactor, the polymer (isotactic propylene type, ethylene type or completely amorphous) for having different crystallinity is also provided in the composition simultaneously.It is also an object of the invention that providing the continuous multi-reactor process condition that this polymer composition can be made effectively to prepare on an industrial scale.

It summarizes

The invention discloses a variety of methods, including, but it is not limited to the continuation method of the elastic composition of Mooney viscosity (ML (1+4)@125 DEG C) of the preparation with 16-180, the composition includes first polymer and second polymer, this method comprises: in the first polymeric area, it polymerize the first monomer system including one or both of propylene and ethylene and propylene in a solvent using the first catalyst system, to provide first polymer, the first polymer has the unit by propylene derived of 60wt% or more, the sequence of propylene derived including isotaxy arrangement and the fusing point for further having the fusing for being lower than 45J/g hot or lower than 105 DEG C are provided simultaneously with both attributes and the Mooney viscosity (125 DEG C of ML (1+4)@) of 1-45；In the second polymeric area, it polymerize the second comonomer system including ethylene or alpha-olefin or both in a solvent using the second catalyst system, to provide second polymer, which is elastomer polymer amorphous or with the crystallinity derived from ethylene；The first polymer and second polymer are merged in the mixture for including solvent and unreacted monomer；And solvent is removed from the mixture, to provide the elastic composition of the Mooney viscosity (125 DEG C of ML (1+4)@) with 16-180.

The invention discloses a variety of methods, including but not limited to prepare the continuation method of the elastic composition containing first polymer and second polymer, this method comprises: in the first polymeric area, it polymerize the first monomer system including one or both of propylene and ethylene and propylene in a solvent using the first catalyst system, to provide first polymer, the first polymer has 60wt% or more by the unit of propylene derived, the sequence of the propylene derived including isotaxy arrangement；In the second polymeric area, polymerize in a solvent using the second catalyst system include ethylene or alpha-olefin or both second comonomer system, to provide second polymer, which is elastomer and amorphous or with the crystallinity for being derived from ethylene；The first polymer and second polymer are merged in the mixture for including solvent and unreacted monomer；Solvent is removed from the mixture, to provide elastic composition；And propylene and vinyl monomer and solvent are recycled；Wherein first polymerization carries out to by propylene monomer being depleted to lower than level needed for preparing the second polymer；Second polymerization and be recycled for vinyl monomer is decreased below prepare the first polymer needed for level, and other supplement propylene monomers are added for the first polymerization, and for the second other make-up ethylene monomers of polymerization addition.This method can be used as tandem reactor or parallel reactor design.

The invention also discloses multiple-stage reactor systems, multiple-stage reactor system including being used to prepare the elastic composition containing first polymer and second polymer, the system includes: the first polymeric area that (a) forms first polymer, which there is at least one to be used to receive the import of the first monomer mixture and solvent at least one for distributing the outlet of the first effluent containing first polymer；(b) there is the second polymeric area for forming second polymer at least one to be used to receive the import of second comonomer mixture and solvent at least one for distributing the outlet of the second effluent containing second polymer；(c) for receive the effluent containing solvent, unreacted monomer, first polymer and second polymer container or other areas；(d) for effluent to be introduced the first effluent Trunk Line in second structure from the first structure, so that the reactor assembly is able to use the effluent Trunk Line and operates in a series arrangement；(e) for making the first effluent bypass the first effluent bypass line of the second reactor, so that the reactor assembly is able to use the effluent bypass line with operation in parallel mode；(f) the second effluent pipeline for introducing effluent from second structure in the third structure.

Also disclose the multiple-stage reactor system for being used to prepare the elastic composition containing first polymer and second polymer, the system includes: the first polymeric area that (a) forms first polymer, which there is at least one to be used to receive the import of the first monomer mixture and solvent at least one for distributing the outlet of the first effluent containing first polymer；(b) the second polymeric area of second polymer is formed, which there is at least one to be used to receive the import of second comonomer mixture and solvent at least one for distributing the outlet of the second effluent containing second polymer；(c) for receive the effluent containing solvent, unreacted monomer, first polymer and second polymer container or other areas；(d) be designed to the recirculation line effluent containing solvent and unreacted monomer being introduced into the first polymeric area and the second polymeric area of first polymeric area or the second polymeric area or serial or parallel connection.

Brief Description Of Drawings

Fig. 1 illustrates an example of the reactor design that can be run in a manner of tandem reactor or parallel reactor.

Detailed description

It is described in detail now, is various definition and performance first, then summarizes specific embodiment, some of them are reflected in the claims, then individually discuss some aspects of required method.

A. definition, performance and test procedure

Various terms used herein are defined below.Even if not being defined on term used in claim below, but it should be given one of ordinary skill in the art for widest definition given by the term, as reflected at least one printed publication (such as dictionary or article), granted patent or published application.

For convenience's sake, many special test programs are indicated to measure the performances such as molecular weight, Mooney viscosity, polydispersity (MWD).However, when those of ordinary skill reads this patent and is desired to determine composition or whether polymer has the particular characteristic indicated in the claims, the program that so can be measured the performance according to any disclosure or generally acknowledged method or test program, but specially indicate is preferred.Each claim be considered as covering any this program as a result, even if distinct program may obtain different result or measured value.Therefore, those of ordinary skill in the art are expected the experiment variation of the measurement performance reflected in detail in the claims.For the property of test method generally, all numerical value are considered " about " or " approximation " specified value,

Continuously.When the one aspect such as processing step for describing method or method, term " continuous " and its derivative include that should cover " continuously " continuous supply and discharge reagent and reaction product, any method or step for allowing to reach stable state, stablizing reaction condition.

It is noncrystalline.Term " noncrystalline " should refer to atactic or unbodied, isotaxy or syndiotaxy (as defined elsewhere herein) should be excluded, should also exclude to have in the case where no annealing can measure fusing point (using DSC program) or produce within one week any material that can measure fusing point after (168 hours) in annealing.

Polymer.Other than required by specific context, terms used herein " polymer " are the products produced in specific aggregation area or reactor by specific continuous polymerization.

Polymerization.Term as used herein " polymerization " should be given those skilled in the art's used widest meaning when indicating to convert polymer for monomer.Polymeric area refers to the region polymerizeing, and is generally formed by the back-mix reactor for being used to form substantially atactic polymer.

It polymerize the ration of division (polysplit).Term as used herein " the polymerization ration of division " should refer to the weight of the first polymer (acrylic polymers) produced by the first polymeric area divided by the calculated result of first polymer and the total weight of second polymer (ethene polymers).The same definition is equally applicable to series connection and parallel reactor configuration.That is, acrylic polymers is always considered as molecule.

Fusing point, fusing heat and crystallization.Polymer and composition as described herein can be characterized with their fusing point (Tm) and fusing heat, and the performance can be influenced by existing for comonomer or the steric impurities for hindering crystallite to be formed by polymer chain.These performances can be by differential scanning calorimetry (DSC) using ASTM E-794-95 (modification of E-794-01) program or in US patent No.6,747,114, the 8th column, the program disclosed in 14-31 row measure, thus which is hereby incorporated by.

Co-monomer content.Co-monomer content and the sequence distribution of polymer can be used¹³C nuclear magnetic resonance spectrometry (NMR) is measured by the way that well known to a person skilled in the art methods.The co-monomer content of discrete molecular weight ranges can be used that well known to a person skilled in the art methods to measure, combination including fourier transform infrared spectroscopy (FTIR) and GPC, such as in Wheeler and Willis, Applied Spectroscopy, 1993, volume 47, described in the 1128-1130 pages.For containing the propylene-ethylene copolymers higher than 75wt% propylene, the co-monomer content (ethylene contents) of this polymer can measure as follows: suppressing uniform and thin film under about 150 DEG C or higher temperature, and be installed on Perkin Elmer PE1760 infrared spectrophotometer.Record the slave 600cm of sample^-1To 4000cm^-1Whole spectrum, the monomer weight percent of ethylene: ethylene wt%=82.585-111.987X+30.045X can be calculated according to following equation², wherein X is in 1155cm^-1The peak height at place in 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, which can be used the program described in Wheeler and Willis to measure.

Steric regularity.Term " steric regularity " refers to the stereoregularity of the orientation of the methyl residues in polymer from propylene." the three unit group steric regularities " of polymer as described herein can as described in US patent No.5,504,172 and US patent No.6,642,316, the 38th row to the 18th row of the 9th column of the 6th column by the polymer¹³C nuclear magnetic resonance (NMR) spectrum measurement；Thus these patents are hereby incorporated by.

Multi-olefin content.The amount for the pendant free olefin being present in the polymer that the amount of the polyene in polymers compositions can be present in after polymerization by quantitative measurment is inferred.Have been established for several programs such as iodine number and use¹H or¹³C NMR measures olefin(e) centent.In the case where polyene is the specific condition of ENB, ASTM D3900 measurement is can be used in the amount for the polyene being present in polymer.The amount of polyene is indicated on the basis of the (for example) total weight of the unit of ethylene and propylene derived.

Tacticity Index.It can pass through here shown as the Tacticity Index of " m/r "¹³C nuclear magnetic resonance (NMR) measurement.Tacticity Index m/r can such as defined in the H.N.Cheng, Macromolecules, 17,1950 (1984) as measure.

Isotaxy, syndiotaxy and atactic.Term as used herein " atactic " is defined as referring to any polymer of Tacticity Index 2.0-4.0.Term as used herein " syndiotaxy " be defined as referring to Tacticity Index be 1.0 to (but not including) 2.0 any polymer.Term as used herein " isotaxy " is defined as referring to any polymer that Tacticity Index is greater than 4.0.

Molecular weight characteristics.The various molecular weight characteristics (such as Mw and Mn) and molecular weight distribution mw/mn (MWD) of polymers compositions (or polymer) as described herein can be according in US patent No.6,525, thus program determination disclosed in 157 the 5th column 1-44 row, the patent are hereby incorporated by.

Mooney viscosity.Term " Mooney viscosity " is here for characterizing the term of certain polymer, polymers compositions and polymer composition.Term as used herein Mooney viscosity (125 DEG C of ML (1+4)@) writes a Chinese character in simplified form " Mooney viscosity " according to the definition described in US patent No.6,686,415 and process of measurement to define and measure；Thus the patent is hereby incorporated by, especially in the 59th row of the 6th column to the text in the 59th row of the 7th column.Alternatively, any " Mooney viscosity " value mentioned herein (including those of in the claims) is considered as including any Mooney viscosity according to any generally acknowledged, disclosed program determination for measuring Mooney viscosity.

Term as used herein " MFR " expression " melt flow rate (MFR) ", and be used to characterize polymer, component and composition.The unit of " MFR " is gram/10 minutes, here for measure the test of MFR with described in ASTM-1238 any modification and condition (at 230 DEG C, using 2.16kg) carry out.

Intermolecular solubility and composition distribution.The other characteristics that may be mentioned in certain claims are " Intermolecular solubility distribution " and " intermolecular composition distribution ".In addition, " being uniformly distributed " used herein is defined as the intermolecular statistically without marked difference of two kinds of distributions of the steric regularity of copolymer composition and polypropylene particularly with certain embodiments of the first polymer.The definition of these terms and the mode for calculating them are disclosed in the 9th column 30-41 row and the 10th column 16-53 row of US patent No.6,525,157；Thus the patent is hereby incorporated by.

B. the specific embodiment of method and composition

Specific embodiment set forth below, some of them are also included in claim.Each single item appended claims define an individually invention, and when encroaching right judgement, it is to be considered as included in various elements or the equivalent of restriction specified in the claim.Depending on context, " invention " all referenced below can only refer to certain specific embodiments in some cases.In other cases, it should be appreciated that " invention " being previously mentioned refers to one or more, but is not necessarily theme described in whole claims.Each single item invention is described more particularly below, including specific embodiment, modification and embodiment, but embodiment that the present invention is not restricted to these, modification or embodiment, their purpose are that those of ordinary skill in the art is enable to realize and utilize the present invention with obtainable information and technology in conjunction with the information in this patent.

In any method described in above or other places, it can be recycled in the first polymeric area or the second polymeric area or the first polymeric area and second polymeric area the two from the solvent and unreacted monomer removed in the mixture.

In any method described in above or other places, during recycling, before being introduced into first or second polymeric area, the solvent and unreacted monomer can be at least partially separate.

In any method described in above or other places, the first polymer for example can have the Mooney viscosity (125 DEG C of ML (1+4)@) of 16-180 and the fusing heat lower than 45J/g or fusing point lower than 105 DEG C or be provided simultaneously with both attributes, and the second polymer has the Mooney viscosity (125 DEG C of ML (1+4)@) of 1-45.

In above or described elsewhere herein any method, the second polymer for example can be the random copolymer of ethylene and propylene.

In above or described elsewhere herein any method, at least part of the effluent of first polymeric area can be introduced continuously into the second polymeric area.

In above or described elsewhere herein any method, at least part of the effluent of first polymeric area can merge with the effluent of the second polymeric area.

In above or described elsewhere herein any method, first and second polymeric area can change into parallel operation mode from serial operation mode, perhaps change into serial operation mode by parallel operation mode or operated with both modes of operation.

In above or described elsewhere herein any method, the polymerization ration of division may, for example, be 5-95.

In above or described elsewhere herein any method, the composition can be the polymerization ration of division with 5-35,16-100 Mooney viscosity (125 DEG C of ML (1+4)@) and 30-80wt% ethylene contents modified EP rubber.

In above or described elsewhere herein any method, the composition can be the modified propylene elastomer of the ethylene contents of the polymerization ration of division with 65-95, the Mooney viscosity (125 DEG C of ML (1+4)@) of 16-45 and 25-50wt%.

In above or described elsewhere herein any method, the mixture containing first polymer and second polymer can by devolatilization come post-processing to form pellet or packing material (bale), recycle unreacted monomer and solvent, and they are recycled to the first and second polymeric areas or the two polymeric areas.

Above or any method described elsewhere herein for example may further include recycling propylene and vinyl monomer and solvent, carry out first polymerization wherein to be consumed to propylene monomer lower than level horizontal needed for preparation second polymer, it wherein carries out the second polymerization and is recycled for level horizontal needed for vinyl monomer to be reduced below to preparation first polymer, and additional make up propylene monomer is added for the first polymerization, addition additional make up ethylene monomer is for the second polymerization.

Above or any method described elsewhere herein for example may further include offer recycle stream, wherein, the score of first polymer produced and the score of second polymer are controlled independently by the amount of the solvent that is supplied to first and second polymerizations of the segmentation from recycling and by providing additional fresh feed with changing the heat-removal capability of flow and each polymerization, this first be aggregated in lower than carried out at a temperature of the fusing point of first polymer and this second be aggregated in than for first polymerization temperature it is 20-200 DEG C high at a temperature of carry out.

In above or described elsewhere herein any method, transfer agent such as hydrogen can be used and carry out restriction molecule amount.

It is sensitive using whether parallel way can correspond to the preselected polymerization ration of division to the polymerization ration of division is determined in above or described elsewhere herein any reactor assembly.

It can be sensitive to the propylene content for determining acrylic polymers using parallel way in above or described elsewhere herein any reactor assembly.

In above or described elsewhere herein any method, changing into parallel way from series system for example can be with the ethylene contents of sensitive determining reactor blend compositions.

In above or described elsewhere herein any method, when polymerizeing the ration of division and being greater than or equal to the C3C2 coefficient for constituting the calculating summation (calculated combination) of FPP (first polymer propylene content) and BPE (blend polymer ethylene content), it is preferable to use parallel way.

In above or described elsewhere herein any method, when the polymerization ration of division is greater than 575* (100-FPP)^0.14*(BPE)^-0.81When, it is preferable to use parallel way, wherein FPP is propylene content (wt% of acrylic polymers), BPE is the ethylene contents of tandem reactor blend composition or parallel reactor blend composition.

Above or any method described elsewhere herein can also comprise the recycle stream being divided into the first recycle stream and the second recycle stream, which is introduced into the first polymeric area and second recycle stream is introduced into the second polymeric area.

Above or any method described elsewhere herein can also comprise most recycle stream being introduced into the second polymeric area.

Above or any method described elsewhere herein can also comprise selection and be enough needed for obtaining (i) the second polymerization temperature；Or the amount of the solvent in the second recycle stream of the polymerization ration of division needed for (ii).

In above or described elsewhere herein any method, solvent is removed from the mixture and unreacted monomer may include that (i) allows the mixture to carry out the first separating step, the stream of polymer is rich in provide the extract from the mixture first rich solvent-laden stream (it can also be defined as the poor stream of first polymer, preferably without or with seldom polymer) and first；(ii) first stream rich in polymer is allowed to carry out the second separating step, the stream for being rich in polymer in order to provide more concentrated second；(iii) merges the solvent-laden stream of the richness, to provide combined recycle stream, for being fed into the first polymeric area or the second polymeric area or the first polymeric area and second polymeric area the two.The solvent-laden stream of the richness can equally contain volatility unreacted monomer.The first step may include liquid separation or evaporation, whether heat.Vacuum can be applied to the stream rich in polymer of the concentration, to extract last trace solvent and monomer.This can by from the polymer material of stirring vacuum extraction complete.The stirring can be provided with film or chain (strand) evaporator, double screw extruder or devolatilizing LIST unit as described elsewhere.

In above or described elsewhere herein any method, solvent is removed from the mixture and unreacted monomer may include that at least part of mixture is carried out liquid phase separation (preferably under high pressure), to provide rich solvent-laden part (poor polymer moieties) and solvent-lean portion (part rich in polymer), wherein the solvent-laden part of the richness (such as recycle stream) is introduced into the first polymeric area or the second polymeric area or first and second polymeric area the two.

In above or described elsewhere herein any method, solvent is removed from the mixture and unreacted monomer may include by at least part of mixture devolatilization, to provide rich solvent-laden part and solvent-lean portion, wherein the solvent-laden part of the richness is introduced into the first polymeric area or the second polymeric area or first and second polymeric area the two, such as a part of recycling.

In above or described elsewhere herein any method, the recycle stream can be introduced into the first polymeric area and the second polymeric area, to provide a kind of recycling ration of division (split), wherein the recycling ration of division is adjusted based in part on the preselected polymerization ration of division or based in part on the temperature of first or second polymeric area.

Above or any method described elsewhere herein can be run by tandem reactor mode, recycle stream is wherein introduced into the first polymeric area and the second polymeric area, to provide a kind of recycling ration of division, wherein the recycle stream percentage of supplied reactor 1 is equal to 2.8* (PS)^0.67*(RT2/RT1)^1.11, wherein PS=polymerize the ration of division；RT2=second reactor temperature (DEG C)；With RT1=first reactor temperature (DEG C).

Above or any method described elsewhere herein can be run by parallel reactor mode, recycle stream is wherein introduced into the first polymeric area and the second polymeric area, to provide a kind of recycling ration of division, wherein the recycle stream percentage of supplied reactor 1 is equal to 4.5* (PS)^0.55*(RT2/RT1)^0.67, wherein PS=polymerize the ration of division；RT2=second reactor temperature (DEG C)；With RT1=first reactor temperature (DEG C).

Compositions disclosed herein is granular or packing material form the composition of total Mooney viscosity (125 DEG C of ML (1+4)@) with 16-180 and the fusing heat lower than 50J/g, it includes first polymer and second polymer, wherein the first polymer is the content of the unit of the propylene derived at least 60% and the elastomeric random polymer of the sequence of the propylene derived including isotaxy arrangement and the fusing heat lower than 45J/g or the fusing point lower than 105 DEG C, the second polymer is the copolymer of no crystallinity or the unit with the crystalline ethylene of ethylene type and propylene derived.

In above or described elsewhere herein certain methods, the Mooney viscosity (125 DEG C of ML (1+4)@) of the composition is 16-180；Or from 16 or 20 or 24 it is any under be limited to 180 or 140 or 120 any upper limit.

In above or described elsewhere herein certain methods, the MFR of the first polymer is 0.5-100g/10min；Or from 0.5 or 0.8 or 1.0g/10min it is any under be limited to any upper limit of 40 or 30 or 20g/10min.

In above or described elsewhere herein certain methods, the MFR of the reactor blend is 0.05-1.3g/10min；Or from 0.05 or 0.06 or 0.07g/10min it is any under be limited to any upper limit of 1.3 or 1.0 or 0.8g/10min.

In above or described elsewhere herein certain methods, the molecular weight (Mw) of the first polymer is 80000-400,000；Or from 100,000 or 120,000 or 140,000 it is any under be limited to 400,000 or 350,000 or 300,000 any upper limit.

In above or described elsewhere herein certain methods, the molecular weight (Mn) of the first polymer is 40,000-200,000；Or from 50,000 or 60,000 or 70,000 it is any under be limited to 200,000 or 175,000 or 150,000 any upper limit.

In above or described elsewhere herein certain methods, the molecular weight (Mw) of the composition is 60,000-800,000；Or from 60,000 or 90,000 or 120,000 it is any under be limited to 800,000 or 700,000 or 600,000 any upper limit.

In above or described elsewhere herein certain methods, the molecular weight (Mn) of the composition is 30,000-160,000；Or from 30,000 or 45,000 or 60,000 it is any under be limited to 160,00 or 140,000 or 120,000 any upper limit.

In above or described elsewhere herein certain methods, the polydispersity (Mw/Mn) of the first polymer is 1.8-2.3；Or from 1.8 or 1.9 or 2.0 it is any under be limited to 2.3 or 2.2 or 2.1 any upper limit.

In above or described elsewhere herein certain methods, the polydispersity (Mw/Mn) of the composition is 1.8-10；Or from 2.2 or 2.0 or 1.8 it is any under be limited to 10 or 6 or 3.5 any upper limit.

In above or described elsewhere herein certain methods, the polymerization ration of division (amount of the first polymer prepared in the first polymerization of the percentage as total composition) is 5-95；Or be limited under 5 or 15 or 25 95 or 80 or 60 the upper limit.

In above or described elsewhere herein certain methods, the first polymer accounts for the 5-95wt% of total composition.

First and second catalyst can be identical；Or they can be different, but in certain embodiments, can have identical activator, as being described in more detail elsewhere herein.In above or described elsewhere herein certain methods, the first catalyst and/or the second catalyst can be metallocene.At a more specific aspect, the first and/or second catalyst is monocyclopentadienyl compound.First and/or second catalyst can be bicyclic pentadiene compounds.The cyclopentadienyl ligands of first and/or second catalyst can be indenyl ligands.First and/or second catalyst can also be Ziegler-Natta catalyst.First and/or second catalyst can also be pyridine amine catalyst.In a specific aspect, the first catalyst can be any catalyst mentioned in PCT Publication WO 03/040201, and that especially mentions is supplied to those of first reactor in double-reactor scheme.Similarly, although the second catalyst can also be any catalyst mentioned in PCT Publication WO 03/040201, more specific second catalyst be mention be supplied to those of second reactor in tandem reactor configuration.

For in terms of broadest, any SSC (single-site catalysts) is can be used to prepare in the composition.This catalyst, which can be, usually contains periodic table 3-10 group 4 transition metal；Keep the transient metal complex for being bonded to the assistant ligand of the transition metal in the course of the polymerization process at least one.Preferably, the transition metal is to restore cationic state use, and is stablized with co-catalyst or activator.

In above or described elsewhere herein any method, first and second catalyst can be unsupported.

In above or described elsewhere herein any method, second catalyst can be selected and be used to introduce the high alpha-olefin that there is no stereoregularity.

In above or described elsewhere herein certain methods, first catalyst is chiral biscyclopentadienyl radical derivative, and second catalyst is achirality bridging fluorenyl cyclopentadiene radical derivative.

In above or described elsewhere herein certain methods, first and second catalyst is used in combination with non-coordinating anion activator, first and second reactors use identical activator, and are optionally accompanied with the derivative containing aluminium of scavenger such as removing.

In above or described elsewhere herein certain methods, the non-coordinating anion is the boron complexes at least two with fused ring system, the preferably ligand of perfluor ring and most preferably four aryl complex.

The isotactic polypropylene fraction that certain compositions as described herein are >=110 DEG C without or with the filler lower than 5wt% and without or with the fusing point lower than 10wt%.

In certain compositions as described herein, total fusing heat of the composition with 1-45J/g.

In certain compositions as described herein, the Mooney viscosity of first polymer is lower than 25 Mooney ML (1+4,125 DEG C), at least ten unit lower than the Mooney ML of total composition (1+4,125 DEG C).

To count on the basis of the combined content of ethylene and the unit of propylene derived, certain compositions as described herein have the total content of the unit of the ethylene derivative lower than 95wt%.

Certain compositions as described herein contain the unit of the ethylene derivative of 40-60wt%, preferably 45wt% or 55wt%.

Certain compositions as described herein have the unit of the ethylene derivative lower than 30wt%.

C. multi-step polymerization

Reaction described herein device blend is formed in continuous " multi-step polymerization ", refers to the different polymerizations (or polymerization stage) of two kinds of progress (or a variety of).More specifically, multi-step polymerization may include two or more sequential polymerizations (also known as " series connection method ") or two or more parallel polymerizations (also known as " parallel method ").

The polymer prepared in each reactor of the continuous multiple reactor solution containment is blended in the form of a solution, is not separated from solvent in advance.The 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 including devolatilization.The blend can also be the product of parallel reactor operation, and the effluent of two of them reactor is merged, and is transported to post-processing step.Any one selection scheme provides the uniform mixing of the polymer in devolatilized blend.Any situation can be made into the various polymerization rations of division, so that the ratio of the amount of the polymer produced in each reactor can change in a wide range.

The first polymer and second polymer of following discussion anabolic reaction device blend composition, are followed by series connection method part, followed by parallel method part.Under suitable occasion, the corresponding difference between series connection and parallel method will be indicated, and otherwise the discussion of series connection method should be considered as being equally applicable to parallel method.

D. first polymer (acrylic polymers)

As described above, here reactor blend preferably at least includes first polymer, the polymer that it is formed in " first reactor " of a part as series connection method or parallel method preferably through the first polymerization reaction (under conditions of described elsewhere herein) and preferably.

As described below, first polymer (being also known as " acrylic polymers " herein) should have (minimum) 50wt% propylene units, preferably more.First polymer should be the unit by propylene derived with >=60wt%, the sequence of the propylene derived with isotaxy arrangement and the acrylic polymers (preferred polypropylene copolymers) hot with the fusing lower than 45J/g.First polymer preferably has the non-propylene co-monomer unit of at least 5wt%, such as ethylene unit, more preferably at least 10wt% or more.The crystallinity of first polymer is generated by isotactic polypropylene sequence.The isotacticity of first polymer can be present in polymer with tri- unit group of mm come illustration with dominant propylene residues.

The crystallinity of first polymer can be indicated with fusing heat.First polymer of the invention can have 1.0J/g or 1.5J/g or 3.0J/g or 4.0J/g or 6.0J/g or 7.0J/g it is any under be limited to 30J/g or 40J/g or 50J/g or 60J/g or 75J/g any upper limit the fusing heat by DSC measurement.Preferably, the fusing heat of first polymer is lower than 45J/g.It is not intended to be restricted by theory, it is believed that first polymer generally has the propylene sequences of isotactic crystallizable, and heat melt above is considered as being attributed to the melting of these crystalline segments.

The crystallinity size of first polymer is also reflected on its fusing point.Preferably, first polymer has single fusing point.However, propylene copolymer sample usually shows the secondary melting peaks adjacent with the main peak.Top is considered as fusing point.First polymer as described herein can have be limited on 115 DEG C or 110 DEG C or 105 DEG C or 90 DEG C or 80 DEG C or 70 DEG C any 0 DEG C or 20 DEG C or 25 DEG C or 30 DEG C or 35 DEG C or 40 DEG C or 45 DEG C any lower limit the fusing point measured by DSC.Preferably, first polymer has lower than 105 DEG C, more preferably less than 100 DEG C, even more preferably less than 90 DEG C of fusing point.Also, it is preferred that first polymer has greater than about 25 DEG C or 40 DEG C of fusing point.

For first polymer, the polymer of at least 75wt% or at least 80wt% or at least 85wt% or at least 90wt% or at least 95wt% or at least 97wt% or at least 99wt% dissolve in single temperature fraction, or dissolve in two adjacent temperatures point, the polymer of remainder dissolves in previous or latter temperature fraction followed by.These percentage are the fractions for example in hexane started at 23 DEG C, and subsequent fraction is the fraction at 23 DEG C or more the increased temperature of increment with about 8 DEG C.Meeting this classification requires the steric regularity for meaning the polypropylene of polymer to have statistically without significant intermolecular differences.

In certain embodiments, as determined by the method with three unit group steric regularities of measurement, the percentage of the tri- unit group of mm in first polymer has 98% or 95% or 90% or 85% or 82% or 80% or 75% any upper limit and 50% or 60% any lower limit.

Certain first polymers have be greater than 0%, or 50% or 25% it is any on be limited to 3% or 10% any lower range in isotacticity index.

The steric regularity (m/r) of certain first polymers can have 800 or 1000 or 1200 any upper limit, and these polymer can have 40 or 60 any lower limit.

As described below, the first polymerization (and second polymerization) can carry out in the presence of alpha-olefin in some cases；In this way, being formed by polymer when there are this alpha-olefin includes by this alpha-olefin " derivative unit ".Identical alpha-olefin or different alpha-olefins can be introduced into the first and second polymerizations.In general, this alpha-olefin preferably has 3-10 carbon atom.The particular instance of these alpha-olefins is C₃-C₂₀Alpha-olefin, 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- neohexenes -1；Heptene -1；Hexene -1；Methylhexene -1；Dimethyl pentene -1；Trimethylbutene -1；Ethylpentene -1；Octene-1；Methylpentene -1；Neohexene -1；Trimethylpentene -1；Ethyl hexene -1；Methylethyl amylene -1；Diethyl -1；Propyl amylene -1；Decylene-1, methyl nonylene-1；Nonylene-1；Dimethyl octene-1；Trimethyl heptene -1；Ethyl octene-1；Methylethyl butene-1；Diethyl -1；Dodecylene -1 and hexadecene -1.

First polymer can optionally include polyene.The optional polyene can be any hydrocarbon structure at least two unsaturated bonds, and wherein at least one unsaturated bond is easy to be introduced in polymer.Second key can be polymerize with subparticipation, form long chain branches, but preferably provided at least some unsaturated bonds suitable for subsequent cure or vulcanization in rear polymerization.The example of optional polyene includes, but it is not limited to butadiene, pentadiene, hexadiene (such as 1, 4- hexadiene), heptadiene (such as 1, 6- heptadiene), octadiene (such as 1, 7- octadiene), nonadiene (such as 1, 8- nonadiene), decadinene (such as 1, 9- decadinene), 11 carbon diene (such as 1, 11 carbon diene of 10-), 12 carbon diene (such as 1, 12 carbon diene of 11-), oleatridecadiene (such as 1, 12- oleatridecadiene), 14 carbon diene (such as 1, 14 carbon diene of 13-), pentadecane diene, 16 carbon diene, 17 carbon diene, 18 carbon diene, 19 carbon diene, 20 carbon diene, 21 carbon diene, 22 carbon diene, two oleatridecadienes, tetracosadiene, two pentadecane diene, 26 carbon diene , heptacosadiene, 28 carbon diene, 29 carbon diene, the polybutadiene of 30 carbon diene and molecular weight (Mw) lower than 1000g/mol.The example of straight chain acyclic diene includes but is not limited to Isosorbide-5-Nitrae-hexadiene and 1,6- octadiene.The example of branched-chain acyclic diene includes but is not limited to 5- methyl-1,4- hexadiene, 3,7- dimethyl -1,6- octadienes and 3,7- dimethyl -1,7- octadiene.The example of single ring alicyclic dienes includes but is not limited to Isosorbide-5-Nitrae-cyclohexadiene, 1,5- cyclo-octadiene and 1,12 carbon diene of 7- ring.The example of polycyclic alicyclic condensed ring and bridging cyclic diene includes but is not limited to tetrahydroindene；Norbornadiene；Methyl tetrahydroquinone；Bicyclopentadiene；Bicyclic-(2.2.1)-hept- 2,5- diene；With alkenyl -, alkylidene radical -, cycloalkenyl-and cylcoalkyliene norbornenes [including such as 5- methylene -2- norbornene, 5- ethidine -2- norbornene, 5- acrylic -2- norbornene, 5- isopropylidene -2- norbornene, 5- (4- cyclopentenyl) -2- norbornene, 5- cyclohexylidene base -2- norbornene and 5- vinyl -2- norbornene].The example for the alkene that cycloalkenyl replaces includes but is not limited to vinylcyclohexene, allyl cyclohexene, vinyl cyclo-octene, 4 vinyl cyclohexene, allyl cyclodecene, vinyl cyclododecene and Fourth Ring (A-11,12) -5,8- dodecylene.

Any first polymer containing ethylene, which preferably has, statistically forms difference without significant intramolecular, which is the ratio of the propylene and ethylene along the segment (intramolecular) of same chain.The composition analysis is inferred to by the method for synthesizing these polymer, can also be passed through¹³CNMR measurement, located the comonomer residues and propylene insertion errors relative to neighboring propylene residues.

First polymer further preferably has statistically without significant intramolecular steric regularity difference, this is attributed to propylene units and is orientated along segment (intramolecular) isotaxy of same chain.The composition analysis is inferred to by the result analyzed in detailed below, and the analysis includes differential scanning calorimetry, electron microscope and relaxation measurement.In the case where steric regularity has significant intramolecular difference, " stereoblock " structure as described below is formd, wherein the number of isotactic propylene residues adjacent to each other is more much bigger than statistics.In addition, the fusing point of these polymer depends on crystallinity, because the polymer for becoming apparent from block-wise should have higher fusing point and the solubility in ambient solvent to reduce.

E. second polymer (ethene polymers)

Reaction described herein device blend includes second polymer component (second polymer), and preferably (or including) has the elastomer of the unit as derived from vinyl monomer more than 30wt% or 40wt% or 50wt% for it.The crystallinity of second polymer is preferably different from those of first polymer with therefore other performance.

Preferably, second polymer (also known as " ethene polymers ") is amorphous, such as atactic or unbodied, but in certain embodiments, and second polymer is crystallization (including " hypocrystalline ").But any crystallinity of second polymer is preferably derived from ethylene, and whether the crystallinity that many disclosed methods, program and technology can be used to evaluate certain material derives from ethylene.By removing first polymer and the then crystallinity of measurement residual second polymer from composition, the crystallinity of the crystallinity of second polymer and first polymer can be distinguished.This crystallinity measured is calibrated and associated with co-monomer content usually using the crystallinity of ceridust.Percent crystallinity in the case of these is measured as the percentage of ceridust crystallinity, and thereby determines that crystallinity from ethylene.

Preferably, other than the unit by ethylene derivative, second polymer further includes the unit as derived from 'alpha '-olefin monomers, in certain embodiments, it is identical as the 'alpha '-olefin monomers for being used to form first polymer, in other embodiments, is at least partially different from the 'alpha '-olefin monomers for being used to form first polymer, in this case, it is referred to as " the second alpha-olefin ".The above any 'alpha '-olefin monomers enumerated in first polymer, especially butene-1, amylene -1, hexene -1, heptene -1 or octene-1 can be used.Advantageously, second polymer can be used selected from above for the different 'alpha '-olefin monomers and/or different amounts of monomer in monomer cited by first polymer, such as ethylene and 'alpha '-olefin monomers are prepared, to prepare different types of second polymer, such as the ethylene elastomer with required performance.Therefore, blend composition can be prepared, wherein the composition includes the first polymer with one group of performance and the second polymer with one group of different performance, in this way, the composition has the expectation mixing or balance of required performance.It can be advantageous to form the composition using continuous multi-stage method (serial or parallel connection), do not need using any separating step, such as removes solvent, such as by devolatilization or do not need physics after releasing and merge polymer.

Preferably, second polymer is formed in (or passing through) second polymerization process, and in the case of series reactors, this is preferably carried out in being located at the reactor for carrying out the downstream for the reactor that first polymerize and formed most of first polymer.In the case where including the parallel method of parallel polymerization and/or parallel reactor, " second polymer " can be formed simultaneously with " first polymer ", but product stream (still including solvent) is merged after being sufficiently formed the first and second polymer.

Preferably, second polymer include (or) elastomer polymer, it preferably has the ethene-alpha-olefin elastomer (including ethylene-cyclic olefin and ethene-alpha-olefin-alkadienes) of high molecular weight (as measuring Mooney viscosity) and low-crystallinity.Second polymer can be with any catalyst appropriate but preferably with following catalyst preparations.In at least one specific embodiment, second polymer is formed in the presence of being different from catalyst (such as " second catalyst ") of the catalyst (such as " first catalyst ") for polymerizeing first polymer.Many second polymers with selection composition (such as monomer type and content) and performance can be formed.

One purpose of first polymer is to improve the characteristic of second polymer.Depending on expected specific application and specific blends, this raising itself can embody in many ways.This improvement for improving including but not limited to following aspect: solidification rate and state；Such as the processing performance as defined in the method for such as grinding, squeezing out, rolling and be molded etc；Physical property such as toughness, viscosity, bonding force, tear resistance, stretching and elongation and such as the heat ageing as defined in the holding at high temperature of this physical property.

Such as, in US patent No.6, any one of ethylene described in 376,610, alpha-olefin, vinyl norbornene elastomer, or any this elastomer (being primarily intended to power cable coating compound) of the ENB as polyene is introduced, it can be used as second polymer and formed.The patent describe the elastomer, their performance and prepare they method part thus in order to which the purpose of US patent working is incorporated by reference.

Also, in US patent No.6, any one of ethylene described in 271,311, alpha-olefin elastomeric polymer composition, or any this elastomer (it is primarily intended to form extruded product) of the ENB as polyene is introduced, it can be used as second polymer and formed.The patent describe the elastomer, their performance and prepare they method part thus in order to which the purpose of US patent working is incorporated by reference.

In addition, second polymer can be in US patent No.5, any one of ethylene described in 807,946, alpha-olefin, vinyl norbornene elastomer, or introduce any this elastomer of the ENB as polyene, it is primarily intended to vehicle part.The patent describe the elastomer, their performance and prepare they method part thus in order to which the purpose of US patent working is incorporated by reference.

In addition, in US patent No.5, any one of ethylene described in 766,713, alpha-olefin, vinyl norbornene elastomer, or any this elastomer (being primarily intended to vehicle hoses) of the ENB as polyene is introduced, it can be used as second polymer and formed.The patent describe the elastomer, their performance and prepare they method part thus in order to which the purpose of US patent working is incorporated by reference.

Also, in US patent No.5,698, any one of ethylene described in 650, alpha-olefin, vinyl norbornene elastomer, or any this elastomer (being primarily intended to vehicle brake parts and power transmission belt) of the ENB as polyene is introduced, it can be used as second polymer and formed.The patent describe the elastomer, their performance and prepare they method part thus in order to which the purpose of US patent working is incorporated by reference.

Furthermore, in US patent No.5, any one of ethylene described in 656,693, alpha-olefin, vinyl norbornene elastomer, or any this elastomer (have and improve curing performance) of the ENB as polyene is introduced, it can be used as second polymer and formed.The patent describe the elastomer, their performance and prepare they method part thus in order to which the purpose of US patent working is incorporated by reference.

Also, in US patent No.5,654, any one of ethylene described in 370, alpha-olefin, non-conjugated bicyclic diene elastomeric polymer, or any this elastomer (then it can be sheet material with calendering is mixed) of the ENB as polyene is introduced, it can be used as second polymer and formed.The patent describe the elastomer, their performance and prepare they method part thus in order to which the purpose of US patent working is incorporated by reference.

Finally, in US patent No.5,571, any one of ethylene described in 883, alpha-olefin, vinyl norbornene elastomer, or any this elastomer (it can be used for being formed motor vehicle vibration damped part) of the ENB as polyene is introduced, it can be used as second polymer and formed.The patent describe the elastomer, their performance and prepare they method part thus in order to which the purpose of US patent working is incorporated by reference.

Therefore, as illustrated in the above patent, second polymer may include one or more optional polyenes, especially include alkadienes；Therefore, second polymer can be ethylene-propylene-diene copolymer (commonly referred to as " EPDM ").The optional polyene is considered to have any hydrocarbon structure of at least two unsaturated bonds, and wherein at least one unsaturated bond is easy to be introduced in polymer.Second key can be polymerize with subparticipation, to form long chain branches, but preferably provide at least some unsaturated bonds of the subsequent cure or vulcanization that are suitable in rear polymerization.The example of optional polyene includes, but it is not limited to butadiene, pentadiene, hexadiene (such as 1, 4- hexadiene), heptadiene (such as 1, 6- heptadiene), octadiene (such as 1, 7- octadiene), nonadiene (such as 1, 8- nonadiene), decadinene (such as 1, 9- decadinene), 11 carbon diene (such as 1, 11 carbon diene of 10-), 12 carbon diene (such as 1, 12 carbon diene of 11-), oleatridecadiene (such as 1, 12- oleatridecadiene), 14 carbon diene (such as 1, 14 carbon diene of 13-), pentadecane diene, 16 carbon diene, 17 carbon diene, 18 carbon diene, 19 carbon diene, 20 carbon diene, 21 carbon diene, 22 carbon diene, two oleatridecadienes, tetracosadiene, two pentadecane diene, 26 carbon diene , heptacosadiene, 28 carbon diene, 29 carbon diene, the polybutadiene of 30 carbon diene and molecular weight (Mw) lower than 1000g/mol.The example of straight chain acyclic diene includes but is not limited to Isosorbide-5-Nitrae-hexadiene and 1,6- octadiene.The example of branched-chain acyclic diene includes but is not limited to 5- methyl-1,4- hexadiene, 3,7- dimethyl -1,6- octadienes and 3,7- dimethyl -1,7- octadiene.The example of single ring alicyclic dienes includes but is not limited to Isosorbide-5-Nitrae-cyclohexadiene, 1,5- cyclo-octadiene and 1,12 carbon diene of 7- ring.The example of polycyclic alicyclic condensed ring and bridging cyclic diene includes but is not limited to tetrahydroindene；Norbornadiene；Methyl tetrahydroquinone；Bicyclopentadiene, bicyclic-(2.2.1)-hept- 2,5- diene；With alkenyl -, alkylidene radical -, cycloalkenyl-and cylcoalkyliene norbornenes [including such as 5- methylene -2- norbornene, 5- ethidine -2- norbornene, 5- acrylic -2- norbornene, 5- isopropylidene -2- norbornene, 5- (4- cyclopentenyl) -2- norbornene, 5- cyclohexylidene base -2- norbornene and 5- vinyl -2- norbornene].The example for the alkene that cycloalkenyl replaces includes but is not limited to vinylcyclohexene, allyl cyclohexene, vinyl cyclo-octene, 4 vinyl cyclohexene, allyl cyclodecene, vinyl cyclododecene and Fourth Ring (A-11,12) -5,8- dodecylene.

F. series connection method

As described above, a kind of form of multi-step polymerization is series connection method (for example, tandem reactor method).Preferably, in the series connection method for including sequential polymerization, two (or multiple) reactors are connected each other " series connection " by conduit (such as pipeline), so that another reactor is fed into from the material (such as effluent) that a reactor is discharged, although valve or other components can be installed between two reactors.Sometimes, two (or multiple) tandem reactors are referred to as single " tandem reactor ".

Preferably, the series connection method be include the continuous solution polymerization method that material is continually introduced into the sequencing equipment group (tandem reactor) by reactor.The reactor apparatus group includes preparation in each comfortable individually reactor of the polymer reactor of at least two series connection (sequence) connections, wherein first polymer and second polymer.(the first and second polymer are further referred to as the first and second polymer " component ".) first reactor can be designed to polymerize first polymer in the solution.Then reactor effluent from first reactor is completely or partially introduced into second reactor, which is designed to polymerize second polymer.This configuration ensures that the second polymer prepared in the second reactor is prepared in the presence of first polymer, which prepares in first reactor.Certainly, it should be realized that, because the reactant polymerizeing in second reactor includes monomer and the first polymer formed completely, so the polymerizate (it is or including " reactor blend compositions ") from second reactor (or in the second reactor) can not only include second polymer, and including one or more polymer materials, one or more polymer materials include or introduce " first polymer " or " second polymer ", but " first polymer " or " second polymer " classification according to any definition of this paper is not fallen into purely.It is noted, however, that being somebody's turn to do " second polymer " but any one of many generally acknowledged analysis methods and technology can be used independently to identify, whether directly measures or calculate.

Generally, unless otherwise prescribed, the polymerization in each reactor can be carried out by any polymerization procedure known in the art, including desired be according to circumstances adjusted optionally or with used equipment.However, it is preferred that be aggregated in reactant and product be completely dissolved in solution under conditions of carry out.These polymerizing conditions can be by using solvent common to enough two kinds of polymer components as polymerisation medium, so that all components of polymeric blends are kept in the solution under suitable reaction condition (including temperature and pressure).

CFSTR.A kind of particularly preferred configuration is at least two continuous flow stirred tank reactor (CFSTR) equipment groups of series connection.The physical structure and construction of this configuration can be conventional in itself.However, each reactor should be able to independently feed monomer, solvent, catalyst etc..In addition, in order to which the qualified stirring for being used as CFSTR and providing should be strong enough, to avoid occurring unmixed zone in reactor.This design consideration of CSFTR is known in those skilled in the art.It is desirable that having removed the polar compound of catalyst poison effect.All solvents and monomer feed can be purified with molecular sieve, bed of aluminium oxide or other absorbents known in the art.In preferred embodiments, in the course of the polymerization process from each reactor except heat.Except heat can be completed by methods known in the art, such as Automatic-cooling, charging precool the various combinations of (adiabatic reactor), cooling coil or these technologies.It is preferred with the adiabatic reactor for precooling charging.

Polymerization temperature.Here a preferred feature for forming the method for reactor blend is the different temperatures for carrying out differential responses (polymerization).Temperature can use equipment well known by persons skilled in the art and program, with one or several Site Determinations of one or several temp probes in reactor.In certain embodiments as described herein, the second polymerization temperature (such as temperature in second reactor) is higher than the first polymerization temperature (such as temperature in first reactor).These temperature hereinbefore provide, a part as specific embodiment.

Reaction pressure.Pressure in each reactor should be enough under the temperature of reactor of selection to keep reactor content in the solution.Preferably, by the first polymerization (such as the polymerization carried out in first reactor) and the second polymerization (such as the polymerization carried out in second reactor) " holding " in specified level or range, mean that polymerization pressure keeps sufficiently constant at least one specific first polymer and/or the production process of reactor blend, it should be apparent that, in the continuous polymerization period, it can be with periodic adjustment, such as in starting, change of rank or maintenance period.Although other pressure or pressure limit can be used in some cases, preferably, first be aggregated in 2100kPa or 1750kPa or 1400kPa or 1050kPa or 700kPa it is any under be limited to 14,700kPa or 13,300kPa or 12,600kPa or 11,900kPa or 11 are carried out under the pressure of any upper limit of 200kPa.Preferably, second polymerization is (in certain embodiments, it is set in and polymerize under identical level with first, or in identical prescribed limit) 2100kPa or 1750kPa or 1400kPa or 1050kPa or 700kPa it is any under be limited to 14,700kPa or 13,300kPa or 12,600kPa or 11, it is carried out under the pressure of any upper limit of 900kPa or 11,200kPa.

Residence time.Term as used herein " residence time " refers to the reactant of the specific aggregation existing average time in particular reactor together with catalyst.This is by calculating reactor volume divided by total volumetric flow rate.Residence time in each reactor depends on many factors, the size including reactor.The example of the residence time of each reactor is 1-180 minutes；Or it is narrower, 5-30 minutes.Although other residence times or residence time ranges can be used in some cases,, but it is preferred that the first residence time was lower limit 4 minutes or 5 minutes or 6 minutes or 7 minutes or 8 minutes or 9 minutes Dao the upper limit 100 minutes or 90 minutes or 80 minutes or 70 minutes or 60 minutes or 50 minutes.Preferably, the second residence time was lower limit 4 minutes or 5 minutes or 6 minutes or 7 minutes or 8 minutes or 9 minutes Dao the upper limit 30 minutes or 25 minutes or 20 minutes or 15 minutes or 12 minutes or 10 minutes.

Monomer.The monomer used in two kinds of polymerizations is illustrated in elsewhere herein, and is determined according to the required composition of particular polymers to be formed.Monomer for example may include ethylene (C₂) and alpha-olefin, including high alpha-olefin (C₄-C₂₀) and polyene, such as non-conjugated diene class.A kind of particularly effective alpha-olefin is propylene, but other high alpha-olefins can be used as described elsewhere herein.

Solvent.As described above, it is preferred to method include polymerisation in solution, this needs solvent.It is hydro carbons that the example of the solvent of (such as being introduced into the first and second reactors) can be used in the first and second polymerization as described herein, such as aliphatic, alicyclic and aromatic hydrocarbons.Preferred solvent is C₁₂Or even lower level linear chain or branched chain saturated hydrocarbons and C₅-C₉It is saturated alicyclic or aromatic hydrocarbons.The example of this solvent is hexane, butane, pentane, heptane, pentamethylene, hexamethylene, cycloheptane, methyl cyclopentane, hexahydrotoluene, isooctane, benzene, toluene and dimethylbenzene.Hexane is preferred.Preferably, in two kinds of polymerizations, such as identical solvent is used in two reactors, and recycle as described below to solvent.

Flow out stream.As described elsewhere herein, in the operating process of continuation method, each reactor is polymerize, and produces outflow stream.The polymer and catalyst and any unreacted monomer that the outflow stream can be generated by polymerization form.The feature of each outflow stream can be with particular polymers concentration.For example, the polymer concentration in each reactor effluent may remain in the range of 1-30wt% or 3-20wt%, counted on the basis of the total weight of specific effluent.As including being illustrated in following embodiment that tandem reactor configures, the polymer concentration of first effluent preferably only indicates first polymer (this can for example be separated by will be formed by polymer with non-polymer material to measure).On the contrary, the polymer concentration of second effluent indicates under given time, such as after the specific residence time or all polymer materials of some other setting time points measurement being present in second reactor.The polymer material includes at least the reactor blend, the reactor blend may include a certain amount of first polymer and at least one other polymer, such as belong to the second polymer of the reaction product of the reaction product of first polymer and other reactants present in the second polymerization process or the reaction product or both forms of other reactants such as monomer itself.Although other polymer concentrations or concentration range can be used in some cases,, but it is preferred that first effluent polymer concentration range is any upper limit being limited in 30wt% or 25wt% or 20wt% or 16wt% or 12wt% or 8wt% under any in 1wt% or 2wt% or 3wt% or 4wt% or 5wt% or 6wt%.Preferably, second effluent polymer concentration range is any upper limit being limited in 30wt% or 25wt% or 20wt% or 18wt% or 16wt% or 14wt% under any in 3wt% or 4wt% or 5wt% or 6wt% or 7wt% or 8wt%.

Polymer recovery.Can and polymer is separated with other ingredients of effluent from any effluent (such as first reactor effluent or second reactor effluent) in recycle polymer.Conventional separate mode can be used.For example, polymer can be recycled from effluent and being condensed with non-solvent such as isopropanol, acetone or n-butanol, or can be by receiving polymer back and forth with heat or steam stripping solvent or other media.One or more conventional additives such as antioxidant can be introduced into polymer in recovery process.Possible antioxidant includes phenyl-β-naphthylamine；Di-tert-butyl hydroquinone, triphenyl phosphate, heptylated diphenylamine, 2,2 '-methylene-bis- (4- methyl-6-tert butyl) phenol and 2,2,4- trimethyl -6- phenyl -1,2- dihydroquinoline.It is also possible to consider other recovery methods for example by using lower critical solution temperature (LCST), subsequent devolatilization.In series connection and parallel configuration, when reactor effluent has been merged, catalyst may be passivated.Passivation should be used to reduce or eliminate the further polymerization out of control in polymer recovery processes downstream.Passivation can be carried out by mixing with suitable polar substances such as water, its residual effect after recycling can be offset with suitable molecular sieve or removing system.

Rate of polymerization.For using the cooling adiabatic reactor as heat removal method of charging, the difference between temperature and feeding temperature that total polymerization rate passes through second reactor is determined.Because refrigeration is improved economic benefits with that can run second reactor and also generate the maximum temperature of the polymer with expected performance such as molecular weight and long chain branching by that can be limited the availability for the commercial refrigeration units that charging is cooled to about -40 DEG C.Therefore, it is intended that second reactor is run at a temperature of more considerably higher than first reactor.The other factors for influencing rate of polymerization (also known as throughput rate) are type of solvent and ratio, monomer type and polymer composition, because heat of polymerization changes with the selection of monomer.

Molecular weight.According to the required performance of reactor blend, molecular weight characteristics (such as Mw, Mn etc.) of adjustable reactor blend and individual first polymer and second polymer (polymers compositions) in some cases.These described elsewhere herein molecular weight characteristics.For example, the molecular weight characteristics of each polymer can be determined by selecting reactor temperature, monomer concentration and by optionally adding chain-transferring agent such as hydrogen.In addition, molecular weight can generally be reduced by improving reaction temperature, and improved by increasing monomer concentration.

G. parallel method

Another form of multi-step polymerization is parallel method (parallel polymerization).In an example of parallel method, two reactors are so that monomer, catalysts and solvents are fed into each reactor independently to configure.Pay attention to, term " first " and " second " do not imply that any certain order or sequence, but the term uses for convenience, so that the word " first " (polymer, polymerization, catalyst, reactor etc.) being mentioned herein can be equally applicable to series connection and parallel method, unless otherwise prescribed.In fact, the first and second polymerizations carry out simultaneously preferably in parallel method.The input object (charging) (preferably carrying out in the first reactor) of first polymerization can be identical as the charging described in the first polymerization of series connection method above, for example including monomer (propylene and one or both of ethylene and 'alpha '-olefin monomers), catalyst mixture and solvent.Output or effluent (such as polymerizate) are also similar to that the effluent of the first polymerization in series connection method, such as first polymer, catalyst, solvent and unreacted monomer, such as propylene monomer.Preferably, the first and second polymerizations use propylene and ethylene as monomer, but ratio is different.

The input object (charging) (preferably carrying out in the second reactor) of second polymerization is identical as the charging described in the second polymerization of series connection method above, but has at least one marked difference, and exactly feeding not includes any first polymer.Another difference is that diene is preferably added to the second polymeric area, such as in reactor.The charging of second polymerization for example may include monomer (ethylene and alpha-olefin), catalyst mixture and solvent.Output or effluent (such as polymerizate) are second polymer, catalyst, solvent and unreacted monomer, such as vinyl monomer.

Specific device is designed, device productivity can be limited by bottleneck provided by recirculating system.For example, polymer and the same polymerization ration of division for isodose, parallel reactor operation usually require to recycle a greater amount of solvents than tandem reactor operation.In addition, parallel reactor operation allows the variation of broader residence time and reactor condition than tandem reactor operation.In tandem reactor operation, by the way that added solvent to be added in second reactor, reach the capacity limit of solvent recycling, the residence time in second reactor can be lower than the residence time in first reactor.It, can be with the residence time of each reactor of independent choice, as long as total solvent flow is no more than recycling capacity with parallel reactor.

It is also an important feature of parallel method using different polymerization temperatures, the discussion above with respect to tandem reactor is equally applicable to parallel system.In addition, the discussion above with respect to the reaction pressure used in tandem reactor method is suitable for parallel method in the same way.In addition, all discussions of the residence time of tandem reactor apply also for parallel reactor.

Flow out stream.As described elsewhere herein, in the operating process of continuation method, each reactor is polymerize, and produces outflow stream.The polymer and catalyst and any unreacted monomer that the outflow stream can be generated by polymerization form.The feature of each outflow stream can be with particular polymers concentration.For example, the polymer concentration in each reactor effluent may remain in the range of 1-30wt% or 3-20wt%, counted on the basis of the total weight of specific effluent.It, can there are three types of flow out stream in parallel reactor, that is, each reactor has one kind, there are also combined outflow stream.Polymer that the polymer concentration of the effluent of each of two reactors preferably indicates only to prepare in the reactor (this can for example be separated by will be formed by polymer with non-polymer material to measure).The polymer concentration of combined effluent indicates under given time, such as after the specific residence time or all polymer materials of some other setting time point measurements being present in two reactors.The polymer material includes at least the reactor blend, the reactor blend may include a certain amount of first polymer and at least one other polymer, such as second polymer or other reactants itself such as monomer reaction product or two kinds of forms reaction product.Although other polymer concentrations or concentration range can be used in some cases,, but it is preferred that first effluent polymer concentration range is lower limit 1wt% or 2wt% or 3wt% or 4wt% or 5wt% or 6wt% to upper limit 30wt% or 25wt% or 20wt% or 16wt% or 12wt% or 8wt%.Preferably, merging effluent polymer concentration range is lower limit 3wt% or 4wt% or 5wt% or 6wt% or 7wt% or 8wt% to upper limit 30wt% or 25wt% or 20wt% or 18wt% or 16wt% or 14wt%.

Polymer recovery.Polymer can be recycled from the effluent of any one reactor or merging effluent and separating polymer with other ingredients of effluent.Conventional separate mode can be used.For example, polymer can be recycled from effluent and being condensed with non-solvent such as isopropanol, acetone or n-butanol, or can be by receiving polymer back and forth with heat or steam stripping solvent or other media.One or more conventional additives such as antioxidant can be introduced into polymer in recovery process.Possible antioxidant includes phenyl-β-naphthylamine；Di-tert-butyl hydroquinone, triphenyl phosphate, heptylated diphenylamine, 2,2 '-methylene-bis- (4- methyl-6-tert butyl) phenol and 2,2,4- trimethyl -6- phenyl -1,2- dihydroquinoline.It is also possible to consider other recovery methods for example by using LCST, subsequent devolatilization.

Rate of polymerization.For using the cooling adiabatic reactor as heat removal method of charging, the difference between temperature and feeding temperature that the total polymerization rate of parallel reactor passes through each reactor is determined.Because refrigeration is improved economic benefits with that can run two reactors and also generate the maximum temperature of the polymer with expected performance such as molecular weight and long chain branching by that can be limited the availability for the commercial refrigeration units that charging is cooled to about -40 DEG C.Influencing rate of polymerization, (other factors of also known as throughput rate are type of solvent and ratio, monomer type and polymer composition, because heat of polymerization changes with the selection of monomer.

H. the series/parallel configuration combined

In a particularly advantageous embodiment, provide including tandem reactor configuration and parallel reactor configuration, and a kind of configuration or another configuration can be configured according to certain standards come the reactor assembly of selection.Such as a kind of method is related to being prepared using series connection method with first group of performance and/or with the reactor blend compositions of corresponding first polymer and second polymer ratio (such as given polymerization ration of division), is then prepared using parallel method with second group of performance and/or with the reactor blend compositions of corresponding first polymer and second polymer ratio (such as given polymerization ration of division).It is preferred that but it is not necessary that, such as the previous reactor blend compositions with first group of performance are carrying out parallel method be discharged before producing latter reactor blend compositions from system.

In certain embodiments, reactor blend compositions are formed using series connection method as described above, for example including the feed polymerization for making the first monomer system with the first catalyst system that can provide isotacticity for the sequence of the unit of propylene derived in a solvent in the first polymeric area, to provide the mixture of first polymer and unreacted monomer, the first polymer is acrylic polymers, with >=60wt% by the unit of propylene derived, the sequence of propylene derived including isotaxy arrangement and the fusing point for further having the fusing for being lower than 45J/g hot or lower than 105 DEG C are provided simultaneously with both attributes and the Mooney viscosity (125 DEG C of ML (1+4)@) of 1-45；And make the merging feed polymerization of first polymer mixture, second comonomer system and the second catalyst system in a solvent in the second polymeric area, to provide the mixture for including first polymer and second polymer, the second polymer is the random copolymer of the unit of ethylene and propylene derived, and wherein the second polymer is amorphous or with ethylene type crystallinity；Wherein: total Mooney viscosity (ML (1+4)@125 DEG C) of the total composition with 25-180 and the fusing heat lower than 50J/g.

Then, according to preassigned, the method can be changed into parallel method (preferably after the reactor blend compositions for removing series process production out of container), and the parallel method may include the feed polymerization for the first catalyst system for making the first monomer system in a solvent in the first polymeric area and capable of providing isotacticity for the sequence of the unit of propylene derived, to provide the mixture of first polymer and unreacted monomer, the first polymer is acrylic polymers, with >=60wt% by the unit of propylene derived, the sequence of propylene derived including isotaxy arrangement and the fusing point for further having the fusing for being lower than 45J/g hot or lower than 105 DEG C are provided simultaneously with both attributes and the Mooney viscosity (125 DEG C of ML (1+4)@) of 1-45；Make the merging feed polymerization of second comonomer system and the second catalyst system in a solvent in the second polymeric area, to provide the mixture for including second polymer, the second polymer is the random copolymer of the unit of ethylene and propylene derived, and wherein the second polymer is amorphous or with ethylene type crystallinity；And in the presence of the solvent merge first polymer and second polymer, wherein Mooney viscosity (ML (1+4)@125 DEG C) of the conjugate of first polymer and second polymer with 25-180 and the fusing lower than 50J/g are hot.

Fig. 1 shows an example of the flow chart of multistage reactor configuration.The flow chart is to illustrate certain methods as described herein (when especially when combined with above observing), including being related between tandem reactor process and parallel reactor process alternately and the method for variable recycle.Device or equipment are indicated each of flow chart box (indicating below), they can be conventional, not need to be described in detail.Connect (following) the expression streams of each line or flow direction of material of box, it should be understood that, stream can have intermediate equipment (not shown) by various types of conduits such as pipeline, these conduits, such as but not limited to modular connection, valve and pump.The content for being related to the WO2002/34795 of reactor and other components is incorporated herein for reference, details especially related with the component such as separator and reactor that exist in this paper Fig. 1.

For at least some embodiments of method described elsewhere herein, total system 10 is shown, it is or including box 12, it can carry out the structure of the first polymerization, and " first reactor " preferably described elsewhere herein.Box 14 is or the structure including that can carry out the second polymerization, and preferably " second reactor ".Box 16 be may include container for receiving the output of one or two of structure 12 and 14 (such as outflow stream 36 and/or 38) and can also include liquid-liquid phase separation equipment structure.Box 18 includes the structure that devolatilization can occur, such as " devolatilizer ".Box 20 is to receive and the structure of discharge monomer and solvent, optionally includes for together or being separately separated the fractionator or some other devices of monomer and solvent.

Polymerization in Fig. 1 can be used as series connection method (i.e. sequential polymerization) or implement as parallel method (such as parallel polymerization).Referring to Fig. 1, the first catalyst can introduce the first polymeric area 12 (such as reactor) via stream 23, usually as a part of catalyst mixture described elsewhere herein.Monomer can introduce polymeric area 12 via stream 26.Fresh monomer can be introduced via stream 28.First polymer (such as acrylic polymers) produces in polymeric area 12.When using arranged in series, propylene effluent (including acrylic polymers) introduces the second polymeric area 14 via stream 34, wherein carrying out the second polymerization to produce second polymer (such as ethene polymers).The effluent (including acrylic polymers and ethene polymers) that the second polymerization is left via stream 36 is introduced into the first separator 16, separating treatment is carried out wherein, such as liquid-liquid phase separation, it is separated to will be enriched in the component of polymer with non-polymeric ingredients (that is, there is no polymer).The non-polymeric ingredients include solvent, unreacted monomer and catalyst.Component rich in polymer preferably mainly comprise polymer composition as described herein, which can be described as containing acrylic polymers and polyvinyl reactor blend.However, should further include the material of such as unreacted monomer (such as propylene, ethylene and diene) not removed in liquid liquid separator successfully etc rich in the component of polymer.Therefore, the component that should be rich in polymer is fed into the second separator, such as devolatilizer 18 via stream 40, and vapor stream 48 and liquid stream 46 is discharged, which has the polymer of higher concentration than the stream 40 before devolatilization.Stream 40 further can be processed suitably, to recycle solvent-free product.Vapor stream 48 including unreacted monomer and solvent is introduced into structure 20, thus monomer and solvent can be discharged via stream 52, or be re-introduced into recycle stream 44 via stream 50.Structure 20 may include one or more fractionator (not shown), can remove vaporized monomers, such as ethylene, propylene and/or diene (such as ENB) alone or in combination whereby.Structure 20 can also include the condenser for converting the vapor contents of stream 48 to liquid.Liquid output stream 50 may include monomer and solvent in some cases, stream 50 can be introduced into the liquid recycle stream 42, the composition of liquid recycle stream 42 optionally can according to be re-introduced into monomer number or amount adjust, to provide recycle stream 44.Recycle stream 44 can be fed into polymeric area 14 again via stream 30, and additional monomer such as ethylene or diene can be added in the input stream 30.Recycle stream 46 can be fed into polymeric area 12 again via stream 26, and additional monomer such as propylene or ethylene can be added in the input stream 26 via stream 28.

As described above, the method in Fig. 1 can be used as parallel polymerization implementation.Change between (above-mentioned) series connection method and the parallel polymerization being discussed below or switch in addition, the configuration in Fig. 1 can permit.With parallel polymerization approach, the outflow stream 34 for leaving the first polymeric area 12 bypasses the second polymeric area 14 preferably via bypass stream 38.Meanwhile monomer is fed into the second polymeric area 14 via input stream 30, which may include the monomer of the fresh monomer from stream 32 and/or a part addition as recycle stream 44.According to parallel configuration, first polymer (acrylic polymers) is not introduced into the second polymeric area 14, but only adds monomer, solvent and catalyst via stream 30 and 24.Second (ethylene) polymer is formed in the second polymeric area, effluent including ethene polymers, unreacted monomer, solvent and catalyst leaves the second polymeric area via stream 36, and (not shown) merges before entering the container (as shown in Figure 1) or alternatively after entering the container with the effluent including first (propylene) polymer from the first polymeric area.As described above, combined effluent includes the polymer composition containing acrylic polymers (being formed in the first polymeric area) and ethene polymers (being formed in the second polymeric area).Certain embodiments are related to the method that different elastic compositions are prepared using same reactor, for example, wherein acrylic polymers and polyvinyl ratio be different or in which acrylic polymers and it is polyvinyl it is respective composition be different.The ratio of the polymer produced in each reactor can change.In one aspect of the invention, one kind is provided for configuring series connection method configuration change (conversion) into parallel method and/or parallel method being configured the device configuration that transformation (conversion) configures into series connection method, is preferably provided according to preassigned.Preferably, parallel method is selected based in part on the one or more of following measured value (and preferred whole) (they can measure (measured in advance) before change or conversion): (a) the preselected polymerization ration of division (adding the total weight of second polymer to calculate divided by first polymer by the weight of first polymer)；(b) propylene content of acrylic polymers (such as first polymer)；(c) ethylene contents of reactor blend compositions (merging of the first and second polymer).Especially preferred embodiment includes forming the first elastic composition with series connection method, and the flow direction for then changing monomer and solvent provides the method for the second elastic composition with the different polymerization rations of division or different monomers (C3 or C2) content to parallel method.Preferably, parallel method is used while polymerizeing the ration of division and being greater than or equal to preselected " C3C2 coefficient ".In a broad sense, C3C2 coefficient is defined as any value for example depending on some calculating summations of FPP (first polymer propylene content) or BPE (blend polymer ethylene content) or both.Preferred C3C2 coefficient is more accurately defined as 575* (100-FPP)^0.14*(BPE)^-0.81(equation 1).Preferably, which is changing into parallel method when polymerizeing the ration of division and being equal to or more than C3C2 coefficient.The accurate timing of change may need not be strict demand, usually polymerizeing ration of division change or just occurring when suggesting that the target polymerization ration of division changed is determined.Following table 1 is shown and the associated different maximum polymerization rations of division of different FPP and BPE values, so that be equal to or more than the shown maximum polymerization ration of division (such as, it is proposed that set point) any polymerization ration of division when should implement parallel method (rather than series connection method).

Table 1

Set point	The maximum polymerization ration of division	FPP (wt%C3)	BPE (wt%C2)
Set point	The maximum polymerization ration of division	FPP (wt%C3)	BPE (wt%C2)	1	46	95	24
2	36	95	40	1	46	95	24
2	36	95	40	3	22	95	64
4	48	88	27	3	22	95	64
4	48	88	27	5	38	88	42
6	23	88	64	5	38	88	42
6	23	88	64	7	50	80	30
8	40	80	44	7	50	80	30
8	40	80	44	9	25	80	65

The following range of blend in table 2 can be produced according to method described herein:

Table 2

First polymer (wt%C2)	Second polymer (wt%C2)	It polymerize ration of division range	Serial or parallel connection
First polymer (wt%C2)	Second polymer (wt%C2)	It polymerize ration of division range	Serial or parallel connection	8-16	40-80	< 20 arrives < 60	Series connection
8-16	40-80	> 20 arrives > 60	It is in parallel	8-16	40-80	< 20 arrives < 60	Series connection

I. it recycles

One particularly advantageous characteristics of certain methods as described herein is variable recycling feature, which contemplates several different modifications (embodiment).In at least one modification of this method, both the quantitative non-polymer from effluent (such as first effluent, second effluent or merging effluent) is introduced into any one or two of the first and second polymeric areas, which is indicated at least some of embodiment with the first and second reactors.Preferably, the amount for being introduced into the non-polymer in the first and second polymeric areas is respectively different from each other.Depending on the property of the first and second polymer, which can be solvent, catalyst or monomer alone or in combination.

Therefore, in a preferred embodiment, the elastic composition including (above-mentioned) first polymer and second polymer is prepared with continuation method.This method preferably includes using identical or different catalyst system (being described in more detail above) and also preferably includes propylene and ethylene but the different monomer system of ratio using for each polymeric area, and first polymer and second polymer are formed in the first and second polymeric areas (serial or parallel connection) in the presence of the solvent of preferably common (identical) solvent respectively.As described above, second polymerization temperature is preferably much higher than the first polymerization temperature, such as high 20 DEG C or more, the second comonomer system for being introduced into the second polymeric area preferably includes diene, it is preferable, however, that not adding diene in the first polymeric area or adding a small amount of diene (lower than 2wt% or lower than 5wt%).This method, which is included in different polymeric areas, polymerize the first and second polymer, and provide include first polymer, second polymer, solvent and unreacted monomer reactor blend.Then, this method includes that solvent and unreacted monomer are removed from reactor blend；Recycle stream containing solvent and unreacted monomer is introduced into the first polymeric area and the second polymeric area；And recycling includes first polymer and second polymer and has 16-180 or the elsewhere herein elastic composition of the Mooney viscosity (125 DEG C of ML (1+4)@) of other horizontal (or the ranges) of defined.

Preferably, the method includes recycle stream is divided into the first recycle stream and the second recycle stream, which is introduced into the first polymeric area and second recycle stream is introduced into the second polymeric area.Preferably, the amount of the solvent in the second recycle stream is selected to obtain to be enough (i) relative to the second polymerization temperature needed for the first polymerization temperature；Or (ii) obtain hereafter with the required polymerization ration of division described elsewhere herein.

As described elsewhere herein, solvent is removed from reactor blend and unreacted monomer may include that (i) allows reactor blend to carry out the first separating step, to provide the first rich solvent-laden part and the second solvent-lean portion；(ii) the first solvent-lean portion is allowed to carry out the second separating step, to provide the second rich solvent-laden part and the second solvent-lean portion；(iii) the first rich solvent-laden part and the second rich solvent-laden part are merged, to provide combined recycle stream；(iv) recycle stream of the merging is introduced into the first polymeric area and the second polymeric area.

Furthermore, solvent is removed from the mixture and unreacted monomer may include that at least part of the mixture is allowed to carry out liquid phase separation, to provide rich solvent-laden part (usually poor polymer moieties) and solvent-lean portion (being usually rich in the part of polymer), wherein the solvent-laden part of the richness is introduced in the first polymeric area and the second polymeric area.

In addition, solvent is removed from the mixture and unreacted monomer may include that at least part of the mixture is allowed to carry out devolatilization, to provide rich solvent-laden part and solvent-lean portion, wherein the solvent-laden part of the richness is introduced in the first polymeric area and the second polymeric area.

Certain embodiments are related to the method for preparing different elastic compositions different using the recycling ration of division between same reactor but reactor.Therefore these methods may include the recirculating mass for being adjusted to different reactor.In a broad sense, " recirculation volume " (term suitable for interval and continuation method) can change.In a continuous process, however, it is to be provided according to certain standards or establish " recirculation rate " (unit time is introduced into the amount in reactor)." recirculation rate " is a generic term, include (a) unit time be fed into two reactors recycle stock total amount (" total recirculation rate ") or (b) unit time is fed into the amount (" first reactor recirculation rate ") of the recycle stock of first reactor or (c) unit time is fed into the amount (" second reactor recirculation rate ") of the recycle stock of second reactor.Under those circumstances, " recycle stock " is defined according at least to solvent, and solvent adds unreacted monomer it is also possible to being, or as the total recycle stream that can also include catalyst recycle.In certain embodiments, any one (lbs or kg/h) of adjustable above-mentioned recirculation rate, for the first recirculation rate is changed into different recirculation rates (such as second rate or third speed etc.) (kg/h)." the recycling ration of division " is defined as first reactor recirculation rate divided by total recirculation rate, can be indicated with (as described below) percentage.

In at least one embodiment, the recycling ration of division is adjusted according at least to the one or more (and preferred whole) of following measured value (they can measure (pre- measurement) before change or conversion): (a) the preselected polymerization ration of division (adding the total weight of second polymer to calculate divided by first polymer by the weight of first polymer)；(b) temperature of the second polymeric area (such as second reactor)；(c) temperature of the first polymeric area (first reactor).

Especially preferred embodiment includes forming the first elastic composition using series connection method, then change the flow of the monomer and solvent that are fed into parallel method, according to above-mentioned standard (i.e. C3C2 coefficient) to provide second elastic composition with the different polymerization rations of division or different monomers (C3 or C2) content；The recycling ration of division is further changed, preferably according to following standard.It is preferable to use regular flow control valves to control the recycling ration of division.

When using any of above series connection method to prepare elastic composition, " the recycling ration of division " is defined as being introduced into the percentage of total recycle solvent of the first polymeric area (such as first reactor), should be indicated with equation 2.The equation indicated with equation 2 should exist at some time points of this method, i.e., in the forming process of elastic composition, it is highly preferred that it keeps (but allowing common technological fluctuation (being higher or lower than the amount) in a continuous process) in the entire method.In equation 2, PS=polymerize the ration of division；RT2=second reactor temperature (DEG C)；And RT1=first reactor temperature (DEG C).Equation 2 provides that the recycle stream percentage of reactor 1 is equal to 2.8* (PS)^0.67*(RT2/RT1)^1.11。

When preparing elastic composition with any of above parallel method, " the recycling ration of division " is defined as being introduced into the percentage of total recycle solvent of the first polymeric area (such as first reactor), should be indicated with equation 3.As equation 2, the equation indicated with equation 3 should exist at some time points of this method, and preferably keep (allowing to fluctuate) in the entire method.In equation 3, PS=polymerize the ration of division；RT2=second reactor temperature (DEG C)；And RT1=first reactor temperature (DEG C).Equation 3 provides that the recycle stream percentage of reactor 1 is equal to 4.5* (PS)^0.55*(RT2/RT1)^0.67。

Tandem reactor is configured, following table 3 is shown and different PS values (the polymerization ration of division) and the associated different recycling rations of division of RT2/RT1 value.Parallel reactor is configured, following table 4 is shown and the associated different recycling rations of division of different PS values and RT2/RT1 value.At least some of embodiment is reflected, each combination is confirmed as a setting value.

Table 3

Setting value	It recycles the ration of division (%)	It polymerize the ration of division	RT2/RT1
Setting value	It recycles the ration of division (%)	It polymerize the ration of division	RT2/RT1	1	44	10	3.0
2	61	10	4.0	1	44	10	3.0
2	61	10	4.0	3	78	10	5.0
4	28	10	2.0	3	78	10	5.0
4	28	10	2.0	5	39	10	2.7
6	50	10	3.3	5	39	10	2.7
6	50	10	3.3	7	21	10	1.5
8	28	10	2.0	7	21	10	1.5
8	28	10	2.0	9	36	10	2.5
10	83	50	2.0	9	36	10	2.5
10	83	50	2.0	11	60	50	1.5
12	83	50	2.0	11	60	50	1.5
12	83	50	2.0	13	93	30	3.0
14	71	20	3.0	13	93	30	3.0
14	71	20	3.0	15	82	25	3.0
16	97	20	4.0	15	82	25	3.0
16	97	20	4.0	17	93	13	5.0

Table 4

Setting value	It recycles the ration of division (%)	It polymerize the ration of division	RT2/RT1
Setting value	It recycles the ration of division (%)	It polymerize the ration of division	RT2/RT1	1	33	10	3.0
2	40	10	4.0	1	33	10	3.0
2	40	10	4.0	3	47	10	5.0
4	25	10	2.0	3	47	10	5.0
4	25	10	2.0	5	31	10	2.7
6	36	10	3.3	5	31	10	2.7
6	36	10	3.3	7	21	10	1.5
8	25	10	2.0	7	21	10	1.5
8	25	10	2.0	9	30	10	2.5
10	62	50	2.0	9	30	10	2.5
10	62	50	2.0	11	51	50	1.5
12	62	50	2.0	11	51	50	1.5
12	62	50	2.0	13	61	30	3.0
14	49	20	3.0	13	61	30	3.0
14	49	20	3.0	15	55	25	3.0
16	59	20	4.0	15	55	25	3.0
16	59	20	4.0	17	54	13	5.0

J. polymerization catalyst

For widest range, any SSC (single-site catalysts) preparation is can be used in the composition.This catalyst, which can be, usually contains periodic table 3-10 group 4 transition metal and at least one transient metal complex for keeping being bonded to the assistant ligand of transition metal in the course of the polymerization process.Preferably, the transition metal is to restore cation state use, and is stablized with co-catalyst or activator.

The assistant ligand can be the structure for being capable of forming pi bond, such as cyclopentadiene base class ring structure.The assistant ligand can also be pyridine or amino ligands.The transition metal is preferably the 4th race's element of periodic table, such as titanium, hafnium or zirconium, they are in polymerization with d⁰Mono-valent cationic state uses, and the assistant ligand being described in detail below with one or two.The important feature of this catalyst for coordination polymerization is the ligand of the ligand that can capture and pluggable ethylene (olefinic) group.

The transient metal complex can be with appropriate chiral to a degree of spatial order of propylene monomer application.In the case where the first polymer for needing higher molecular weight or higher polymerization temperature, preferably noncoordinating or Weakly coordinating anions (term as used herein non-coordinating anion includes Weakly coordinating anions) are used as co-catalyst.Alternatively, it can be used and introduce oxygen-constructed of aluminium part aikyiaiurnirsoxan beta or complex.

The precursor of non-coordinating anion can be used together with the transient metal complex for restoring valence state supply.The precursor can carry out redox reaction.The precursor can be neutrality, such as borane complexes, and can be by forming transition-metal cation from the precursor abstractable ligand.The precursor can be the ion pair that precursor cation such as borate is neutralized and/or eliminates in some manner.The precursor cation can be such as the ammonium salt described in EP 277 003 and EP277 004.The precursor cation can be such as the triphenylcarbenium derivative described in EP 426 637.Non-coordinating anion can be 10-14 race complex, wherein boron or aluminium be can by halogenation, the electrically charged atom of especially fluorinated ligand shielding.It is preferred that the 10-14 race non-carbon element type anion that four aryl replace, those of the hydrogen atom on especially fluorine-based substituted aryl or the hydrogen atom on the alkyl substituent of these aryl.

The non-coordinating anion can relative to the about equimolar amounts of transient metal complex, for example, at least 0.25, preferably 0.5, especially 0.8 and the amount for example no more than 4, preferably 2 and especially 1.5 use.

The transient metal complex can be the pyridine amine complex for olefinic polymerization, such as those of described in WO 03/040201.The transient metal complex, which can be, reset in periodic molecular, in order to provide the fluxional complex that required steric regularity is interrupted, such as in Waymouth, US patent No.6, those of described in 559,262.The transient metal complex can be the stereorigid complex as having mixed influence to propylene insertion described in Rieger EP1 070 087.

Preferably, the transient metal complex is the chiral bridging biscyclopentadienyl derivative with following general formula:

L^AL^BL^C _iMDE

Wherein L^AAnd L^BIt is the substituted or unsubstituted cyclopentadienyl group or heterocyclic pentylene base assistant ligand that M is connected to pi bond, wherein L^AAnd L^BLigand by the 14th race's element linker with covalent bond bridging together, L^C _iIt is with the optional neutrality for being connected to M with coordinate bond, non-oxidizing ligand (i is equal to 0-3)；M is the 4th or 5 group 4 transition metals；D and E is independently the unstable ligand of single anion, is respectively keyed with σ in M, optionally mutual bridging or and L^AOr L^BBridging.Single anion ligand be it is replaceable by suitable activator, to allow polymerisable monomer or macromonomer to be inserted into, to carry out coordination polymerization in the free coordination site of transition metal component.

When a catalyst is used, total catalyst system generally also comprises one or more organo-metallic compounds as scavenger.Such compound as used in this application is intended to include removing those of polar impurity and raising catalyst activity compound effectively from reaction environment.

In at least one embodiment, polymerization comprises the steps of or the following steps are included: polymerize in the presence of including the catalyst of bis- (cyclopentadienyl group) metallic compounds and (1) noncoordinating compatible anion activator or (2) alumoxane activator.The non-limiting example for the catalyst system that can be used is described in US patent Nos.5,198,401 and 5,391,629, thus the disclosure of which is incorporated herein by reference.In a particular aspects of the embodiment, alumoxane activator can be to provide 1: 1 to 20,000: 1 aluminium and the amount use of metallocene molar ratio.In another particular aspects of the embodiment, noncoordinating compatible anion activator can be used with the amount for providing 10: 1 to 1: 1 biscyclopentadienyl compound and the molar ratio of non-coordinating anion.In another particular aspects of the embodiment, the polymerization reaction include allow monomer in the presence of catalyst system as described herein -0 DEG C to 200 DEG C at a temperature of 1 second to 10 hours time of reaction.

In certain embodiments, first polymer of the invention can be prepared in the presence of chiral metallocene catalyst and activator and optional scavenger.The uniformity of polymer is improved it is preferable to use single centre metalloscene catalyst.Because only needing limited steric regularity, it is possible to use many various forms of single-site catalysts.Possible single-site catalysts are metallocenes, such as in US patent No.5,026, those of described in 798, they have single cyclopentadienyl rings, are advantageously substituted and/or form a part of multiring structure, and hetero atom (usual nitrogen-atoms, it is also possible to being phosphorus atoms or phenoxy group) it is connected to the 4th group 4 transition metal, preferably titanium, but may be zirconium or hafnium.Another example is with B (CF)₃The Me of activation₅CpTiMe₃, it is used to prepare the elastomeric polypropylene of the Mn at most 4,000,000.Referring to Sassmannshausen, Bochmann, Rosch, Lilge, J.Organomer.Chem. (1997) 548,23-28.

Other possible single-site catalysts are the metallocenes for belonging to the biscyclopentadienyl derivative with magnesium-yttrium-transition metal, preferably hafnium or zirconium.This metallocene can be it is non-bridged, such as US patent No.4,522,982 or US patent No.5, described in 747,621.The metallocene may be adapted to the polymer of the main unit including propylene derived of preparation, such as US patent No.5,969,070, and which prepares homogeneous polymers of the fusing point higher than 79 DEG C using bis- (2- phenyl indenyl) zirconiums of non-bridged dichloro.The cyclopentadienyl rings can be a part that is substituted and/or being polycyclic system, as described in the above US patent.

Other possible metallocenes include that two of them cyclopentadienyl group is connected by abutment, usually monatomic abutment such as silicon or carbon atom and group is selected to occupy those of two residual valences.This metallocene is described in the following documents: US patent No.6,048,950 (it discloses bis- (dimetylsilyl) zirconiums of dichloro bis- (indenyls)) and MAO)；WO98/27154 (it discloses double indenyls of dimethylsilyl base bridging to close hafnium and non-coordinating anion activator)；EP1 070 087 (it discloses the bridging biscyclopentadienyl catalysts between two cyclopentadienyl ligands with asymmetric element, for obtaining flexible polymer).The metallocene is also illustrated in US patent Nos.6,448,358 and 6,265,212.

The activation method of single-site catalysts can change.Aikyiaiurnirsoxan beta and preferred methylaluminoxane can be used.High molecular weight is obtained using noncoordinating or Weakly coordinating anions activator (NCA) that is derivative in a manner of any described in patent document such as EP277 004, EP426 637 etc. and generating.It is generally acknowledged that activation includes capturing anionic group such as methyl, to form metallocene cations, but according to certain documents, amphoteric ion can produce.NCA precursor can be the ion pair of borate or aluminate, and wherein precursor cation is eliminated when activating in some manner, for example, the trityl or ammonium derivative (referring to EP277 004) of four (pentafluorophenyl group) boron.The NCA precursor can be neutral compound, such as borine, it forms cationic (referring to EP426 638) and capturing and introducing the anionic group captured from metallocene.

K. specific catalyst

As described elsewhere herein, in certain embodiments, the polymerization in different reactor can carry out in the presence of identical catalyst mixture, and in other embodiments, it can be carried out in the presence of different catalyst mixtures.Term as used herein " catalyst mixture " (catalyst system) includes at least one catalyst and at least one activator, but depends on context, and " catalyst " mentioned in this article usually also implies activator.

Catalyst mixture appropriate can be transported to corresponding reactor in various ways.For example, it can be used as solution or slurry is delivered independently to reactor, is just activated in the pipeline before reactor or pre-activate and be pumped into reactor as activated solution or slurry.It is aggregated in each reactor and carries out, wherein reactant component (example monomer as required, comonomer, catalyst/activator, scavenger and optional modifying agent) is preferably added continuously in reactor appropriate.In certain embodiments, two kinds of catalyst mixtures are added in first reactor, and in other embodiments, a kind of catalyst mixture is added in first reactor, different catalysts mixture is added in second reactor to (although in subsequent operation, at least some first catalyst mixtures from first reactor can be introduced together into second reactor with the product mixtures from first reactor.

In preferred embodiments, a part addition that two kinds of different catalysts are fed as differential responses agent, such as " the first catalyst " can be a part of " charging of the first reactant ", " the second catalyst " can be a part of " charging of the second reactant ", but at least some embodiments (such as tandem reactor), first and second catalyst are in second reactor charging simultaneously there is (for example, when first effluent is supplied second reactor) to a certain degree.Preferably, at least some embodiments, the first catalyst is chiral catalyst, and the second catalyst is achiral catalyst.

In the method and certain embodiments of composition, identical catalyst mixture is respectively can be used in whether the first and second polymerizations of series connection or parallel connection.For example, US patent No.6 can be used in two kinds of polymerizations in certain methods, thus certain catalyst mixtures described in 207,756, the patent are hereby incorporated by, the part of catalyst mixture especially described, such as the 20th row of the 8th column is to the 21st row of the 14th column.Preferred catalyst be isotactic (isospecific) those.The process for forming the specific example of useful catalyst system provides in the embodiment 1 of the patent.

First catalyst.First catalyst is preferably chiral catalyst.In at least one specific embodiment, first is aggregated in the presence of the first catalyst for belonging to " single centre polymerization catalyst " and carries out, which preferably only allows to add two kinds of different monomers sequences, such as propylene sequences and ethylene sequence by single statistical.First catalyst is preferably sufficiently mixed in continuous flow stirred tank polymer reactor, so that only providing single polymerization environment for the essentially all of polymer chain of the polymer.It is preferred that by first activation of catalyst, it is meant that it is in some manner in conjunction with activator.

As at least one example, the first catalyst may include bis- (cyclopentadienyl group) metallic compounds, and can be in conjunction with (1) noncoordinating compatible anion activator or (2) alumoxane activator.(all " catalyst " mentioned herein it is also preferable to include activators, unless otherwise prescribed.) non-limiting example of catalyst system (including activator) that can be used is described in US patent Nos.5,198,401 and 5,391,629, thus disclosures of which is incorporated herein by reference.In a particular aspects of the embodiment, alumoxane activator can be to provide 1: 1 to 20,000: 1 aluminium and the amount use of metallocene molar ratio.In another particular aspects of the embodiment, noncoordinating compatible anion activator can be used with the amount for providing 10: 1 to 1: 1 biscyclopentadienyl compound and the molar ratio of non-coordinating anion.In another particular aspects of the embodiment, the polymerization reaction include allow monomer in the presence of catalyst system as described herein -0 DEG C to 200 DEG C at a temperature of 1 second to 10 hours time of reaction.

Second catalyst.Second catalyst (if being different from the first catalyst) is preferably achiral catalyst, is further preferably sufficiently mixed in continuous flow stirred tank reactor.It is preferred that by second activation of catalyst, it is meant that it is in some manner in conjunction with activator.The example of second catalyst is described in elsewhere herein, and is also described in WO00/24793, thus which is incorporated by reference.

Embodiment

Following examples set forth the methods that the continuous polymerization of the continuous flow stirred tank reactor progress by using two arranged in series forms the reactor blend being made of two distinct types of polymer, to two reactor continuous feed different monomers mixtures and catalyst mixture.Hexane solvent is fed into each reactor, so that the content of each reactor is kept in the solution.The temperature of second reactor is apparently higher than first reactor.Then each catalyst stream is fed into respective reaction device using metering pump to prepare by the way that catalyst and activator to be pre-mixed in 900ml toluene.Catalyst mixture A (being fed into reactor 1) is the mixture that unsupported dimethylsilyl base bis- (indenyls) closes hafnium catalyst and four (pentafluorophenyl group) boron dimethylaniline activators.Catalyst mixture B (being fed into reactor 2) is such as in US patent No.6, unsupported dimethyl two-(p- triethylsilyl benzyl) carbyl (cyclopentadienyl group) (2-7 di-t-butyl fluorenyl) disclosed in 506,857 (catalyst A) embodiments 1 and 4 closes the mixture of hafnium and the identical activator used in catalyst mixture A.Catalyst adding rate is given in Table 5.Use tri-n-octylaluminium as scavenger in reactor 1.

Table 5

Reactor	Can wt.(g)	The Can time (min)	Catalyst mixture	Catalyst rates	Scavenger	Hydrogen (g/h)	C₂ (g/h)	C₃ (g/h)	ENB (g/h)	C₆ (g/h)	T (℃)
Reactor	Can wt.(g)	The Can time (min)	Catalyst mixture	Catalyst rates	Scavenger	Hydrogen (g/h)	C₂ (g/h)	C₃ (g/h)	ENB (g/h)	C₆ (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	1	534	10	A	0.00233	0.118	0	12	199.8	0	3564	47

Table 6

Reactor	Throughput rate (g/hr)	It polymerize the ration of division (%)	C₂Conversion ratio (%)	C₃Conversion ratio (%)	ENB conversion ratio (%)
Reactor	Throughput rate (g/hr)	It polymerize the ration of division (%)	C₂Conversion ratio (%)	C₃Conversion ratio (%)	ENB conversion ratio (%)	1	74.6	26	134	29	N/R
2	289.6		74	44	48	1	74.6	26	134	29	N/R

The effluent of reactor 1 polymerization including first polymer product.The effluent including unreacted monomer and catalyst mixture is fed into reactor 2, is polymerize under the conditions of differential responses herein.For example, using considerably higher temperature of reactor in reactor 2.In addition, introducing polyene (5- ethidine -2- norbornene).The throughput rate of each reactor evaporates solvent and measurement remaining solid concentration then by timed collection effluent to determine.The throughput rate of reactor 1 is by stopping the reaction in reactor 2 and then being determined using the effluent of the same processes timed collection reactor 1.When two reactors are fully-operational, total throughput rate is measured using the output of reactor 2 according to same processes.Using the information, the ratio of reactor 1 throughput rate and total throughput rate is calculated.The ratio is referred to as " the polymerization ration of division " in table 6.Using catalyst make-up and feed rate and throughput rate, catalyst productivity (g polymer/g catalyst) is calculated by catalyst efficiency.

The various performances of the polymer product formed in each reactor are reported in table 7 and 8.As seen in Table 7, the polymer formed in reactor 1 has the ethylene contents of 21wt%.On the contrary, the polymer product being discharged from reactor 2 has a 61wt% ethylene contents, the polymer product be include reactor blend that the polymer formed in reactor 1 adds the other polymer formed in reactor 2.The ethene value of the second polymer calculated by first polymer and reactor blend ethylene contents and the polymerization ration of division is 75%.The value of ENB is 6.9%.The other measurement performances reported include that (g ' and BI) all reflects in table 7 and 8 for Mooney viscosity, melt index (MI), molecular weight data and branching measurement.

Table 7

Reactor	C₂(%)	ENB (%)	ML (1+4@125℃)	MI	The small angle laser light scattering (Lalls) of Mw	The small angle laser light scattering of Mz	Mw DRI
Reactor	C₂(%)	ENB (%)	ML (1+4@125℃)	MI	The small angle laser light scattering (Lalls) of Mw	The small angle laser light scattering of Mz	Mw DRI	First polymer	21	0		4.2	1697 37	2704 19	1639 66
Second polymer	75	6.9						First polymer	21	0		4.2	1697 37	2704 19	1639 66
Second polymer	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	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	Reactor 1	83646	0.963	0.963	2.03	1.59

Claims

1, the continuation method of the elastic composition of Mooney viscosity (ML (1+4)@125 DEG C) of the preparation with 16-180, the composition includes first polymer and second polymer, this method comprises:

In the first polymeric area, it polymerize the first monomer system including propylene and optional ethylene in a solvent using the first catalyst system, to provide first polymer, unit by propylene derived of the first polymer with 60wt% or more, the sequence of the propylene derived including isotaxy arrangement and the fusing point for further having the fusing for being lower than 45J/g hot or lower than 105 DEG C are provided simultaneously with both attributes and the Mooney viscosity (125 DEG C of ML (1+4)@) of 1-45；

In the second polymeric area, it polymerize the second comonomer system including ethylene and optional alpha-olefin, optimal ethylene in a solvent using the second catalyst system, to provide second polymer, which is elastomer polymer amorphous or with the crystallinity derived from ethylene；

The first polymer and second polymer are merged in the mixture for including solvent and unreacted monomer；And

Solvent and unreacted monomer are removed from the mixture, to form the recycling for the first polymeric area or the second polymeric area, or the recycling for being used for both the first polymeric area and second polymeric area is formed, and provide the elastic composition of the Mooney viscosity (125 DEG C of ML (1+4)@) with 16-180.

2, according to the method described in claim 1, wherein the solvent and unreacted monomer are separated at least partially in front of being introduced into first or second polymeric area.

3, method according to claim 1 or 2 is used to prepare level horizontal needed for second polymer so that propylene monomer to be consumed to be lower than wherein carrying out first polymerization；It carries out second polymerization and is recycled for for 'alpha '-olefin monomers being reduced below level horizontal needed for being used to prepare first polymer, and for the first polymerization addition additional make up propylene monomer, and for the second polymerization addition additional makeup alpha-olefin monomer.

4, the continuation method of the elastic composition containing first polymer and second polymer is prepared, this method comprises:

In the first polymeric area, it polymerize the first monomer system including propylene and optional ethylene in a solvent using the first catalyst system, to provide first polymer, which has the unit by propylene derived of 60wt% or more, the sequence of the propylene derived including isotaxy arrangement；

In the second polymeric area, polymerize the second comonomer system including ethylene and optional alpha-olefin in a solvent using the second catalyst system, to provide second polymer, the second polymer be elastomer and it is amorphous or be derived from ethylene crystallinity；

The first polymer and second polymer are merged in the mixture for including solvent and unreacted monomer；

Solvent and propylene and vinyl monomer are removed, from the mixture to provide elastic composition；And

Propylene and the recycling of vinyl monomer and solvent are used to polymerize；Wherein:

First polymerization carries out extremely being depleted to propylene monomer to be lower than being used to prepare level horizontal needed for the second polymer；

It second polymerization and is recycled for vinyl monomer to be decreased below to level horizontal needed for being used to prepare the first polymer, and for the first polymerization addition additional make up propylene monomer, and for the second polymerization addition additional make up ethylene monomer.

5, according to the method described in claim 4, wherein the first polymer has the fusing heat lower than 45J/g or the fusing point lower than 105 DEG C or is provided simultaneously with both attributes and the Mooney viscosity (125 DEG C of ML (1+4)) of 1-45；And the elastic composition has the Mooney viscosity (125 DEG C of ML (1+4)@) of 16-180.

6, according to described in any item methods of preceding claims, wherein the second polymer is the random copolymer of ethylene and propylene and optional diene.

7, according to described in any item methods of preceding claims, wherein in operation in series mode, at least part of the effluent of first polymeric area is introduced continuously into the second polymeric area, and/or in operation in parallel mode, at least part of the effluent of first polymeric area is merged with the effluent of the second polymeric area.

8, according to described in any item methods of preceding claims, wherein the polymer phase produced in first polymeric area is 5-95 to the polymerization ration of division of the total polymer produced in the first and second polymeric areas.

9, according to described in any item methods of preceding claims, including the mixture of first polymer and second polymer by devolatilization come post-processing, to form pellet or packing material.

10, according to described in any item methods of preceding claims, wherein the score of first polymer produced and the score of second polymer are controlled independently by the amount of the solvent that is supplied to first and second polymerizations of the segmentation from recycling and by providing additional fresh feed with changing the heat-removal capability of flow and each polymerization, this first be aggregated in lower than carried out at a temperature of the fusing point of first polymer and this second be aggregated in than for first polymerization temperature it is 20-200 DEG C high at a temperature of carry out.

11, according to described in any item methods of preceding claims, wherein limiting the molecular weight in first or second polymeric area using transfer agent.

12, according to described in any item methods of preceding claims, wherein, when the polymerization ration of division of the polymer phase produced in the first polymeric area to the total polymer produced in the first and second polymeric areas is greater than or equal to the C3C2 coefficient for constituting the calculating summation of FPP (first polymer propylene content) and BPE (blend polymer ethylene content), the method is run with parallel way.

13, according to described in any item methods of preceding claims, wherein when the polymerization ration of division of the polymer phase produced in the first polymeric area to the total polymer produced in the first and second polymeric areas is greater than 575* (100-FPP)^0.14*(BPE)^-0.81When, the method is run with parallel way, and wherein FPP is propylene content (wt% of acrylic polymers), and BPE is the ethylene contents of tandem reactor blend composition or parallel reactor blend composition.

14, according to described in any item methods of preceding claims, the recycle stream is wherein divided into the first recycle stream and the second recycle stream, which is introduced into the first polymeric area and second recycle stream is introduced into the second polymeric area.

15, according to the method for claim 14, wherein selection is enough needed for obtaining (i) the second polymerization temperature；Or the amount of the solvent in the second recycle stream of the polymerization ration of division needed for (ii).

16, according to described in any item methods of preceding claims, wherein remove solvent from the mixture and unreacted monomer includes that (i) allows the mixture to carry out the first solvent separating step, the polymer for being concentrated in residual solvent；(ii) concentrate solution is allowed to carry out second step, for further removing solvent and forming the molten polymer of granulation；(iii) merges the solvent extracted from the first and second steps, to provide combined recycle stream；(iv) recycle stream of the merging is introduced into the first polymeric area or the second polymeric area or the first polymeric area and second polymeric area the two.

17, according to the method for claim 16, wherein the first step includes that at least part of the mixture is allowed to carry out liquid-liquid phase separation, to provide rich solvent-laden part and solvent-lean portion.

18, -11 described in any item methods according to claim 1, wherein the method is run by tandem reactor mode, and recycle stream is wherein introduced into the first polymeric area and the second polymeric area, to provide a kind of recycling ration of division, wherein the recycle stream percentage of supplied reactor 1 is equal to 2.8* (PS)^0.67*(RT2/RT1)^1.11, the polymerization ration of division of the polymer phase wherein produced in the first polymeric area of PS=to the total polymer produced in the first and second polymeric areas；RT2=second reactor temperature (DEG C)；With RT1=first reactor temperature (DEG C).

19, -11 described in any item methods according to claim 1, wherein the method is run by parallel reactor mode, and recycle stream is wherein introduced into the first polymeric area and the second polymeric area, to provide a kind of recycling ration of division, wherein the recycle stream percentage of supplied reactor 1 is equal to 4.5* (PS)^0.55*(RT2/RT1)^0.67, the polymerization ration of division of the polymer phase wherein produced in the first polymeric area of PS=to the total polymer produced in the first and second polymeric areas；RT2=second reactor temperature (DEG C)；With RT1=first reactor temperature (DEG C).

20, it is used to prepare the multistage reactor device of the elastic composition including first polymer and second polymer, which includes:

(a) include the first structure to form the first polymeric area of first polymer, the first structure have at least one be used to receive the import of the first monomer mixture and solvent and at least one for distributing the outlet of the first effluent containing first polymer；

It (b) include the second structure to form the second polymeric area of second polymer, which has that at least one is used to receive the import of second comonomer mixture and solvent and at least one is used to distribute the outlet of the second effluent containing second polymer；

(c) third structure, the third structure include the container for receiving the effluent containing solvent, unreacted monomer, first polymer and second polymer；

(d) for effluent to be introduced the first effluent Trunk Line in second structure from the first structure, so that the reactor assembly is able to use the effluent Trunk Line and operates in a series arrangement；

(e) for making the first effluent bypass the first effluent bypass line of the second reactor, so that the reactor assembly is able to use the effluent bypass line with operation in parallel mode；With

(f) the second effluent pipeline for introducing effluent from second structure in the third structure.

21, device according to claim 20, wherein the system is used to carry out according to claim 1-19 described in any item methods.

22, the device according to claim 20 or 21, wherein the first and second polymeric areas interconnection, to allow to change into operation in parallel mode from operation in series mode, or the combination of operation in series mode or series system and parallel way is changed into from operation in parallel mode.

23, total Mooney viscosity (ML1+4 with 16-180,125 DEG C of@) and granular or packing material form the composition hot lower than the fusing of 50J/g, it includes first polymer and second polymer, the first polymer is the sequence of the content of the unit of the propylene derived at least 60% and the propylene derived including isotaxy arrangement and the elastomeric random polymer with the fusing heat lower than 45J/g or the fusing point lower than 105 DEG C, which is the copolymer of the unit of nodeless mesh degree or ethylene and propylene derived with ethylene type crystallinity.

24, composition according to claim 23, wherein the composition is the modified EP rubber with the polymer of 5-35wt%, the polymer by the unit of propylene derived, the sequence of propylene derived including isotaxy arrangement and the fusing point further with the fusing heat for being lower than 45J/g or lower than 105 DEG C or is provided simultaneously with both attributes and the Mooney viscosity (125 DEG C of ML (1+4)@) of 1-45 with 60wt% or more, the ethylene contents of the rubber Mooney viscosity (125 DEG C of ML (1+4)@) and 30-80wt% with 16-100.

25, composition according to claim 23, wherein the composition is the modified propylene elastomer with the polymer of 65-95wt%, the polymer is with 60wt% or more by the unit of propylene derived, the sequence of propylene derived including isotaxy arrangement and the fusing point further with the fusing heat for being lower than 45J/g or lower than 105 DEG C or the Mooney viscosity for being provided simultaneously with both attributes and 1-45 (125 DEG C of ML (1+4)@), the ethylene contents of the composition Mooney viscosity (125 DEG C of ML (1+4)@) and 25-50wt% with 16-45.