CN103443199B

CN103443199B - The alkene triblock polymer obtained by ring-opening metathesis polymerization

Info

Publication number: CN103443199B
Application number: CN201280014779.1A
Authority: CN
Inventors: I·C·斯图尔特
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2011-03-25
Filing date: 2012-03-05
Publication date: 2016-04-06
Anticipated expiration: 2032-03-05
Also published as: WO2012134713A3; CN103443199A; EP2688954A2; EP2688954A4; WO2012134713A2; WO2012134713A8

Abstract

The present invention relates to containing using following formula: PO-(-C=C-Z-) _n-C=C-PO* (I) or PO-(-C-C-Z-) _nthe composition of many block polyolefin that-C-C-PO* (la) represents, wherein Z is a part for the cyclic monomer with at least one internal double bond, and this part retains after ring-opening metathesis reaction; PO and PO* is polyolefine independently of one another; Be 1-about 10 with n, 000; With the method for this composition of preparation, the method comprises the polyolefinic dimer making olefin metathesis catalyst and ethenyl blocking, contacts with the cyclic hydrocarbon group monomer containing at least one internal double bond.

Description

The alkene triblock polymer obtained by ring-opening metathesis polymerization

Priority request

This application claims rights and interests and the right of priority of the EP11167037.8 that the USSN13/072432 and 2011 that submits on March 25th, 2011 submits to 23, on Mays.

Invention field

The present invention relates to and prepare triblock polymer by the polyolefine transposition of ethenyl blocking.

Background of invention

Transposition is considered to be in the exchange of free radical between two kinds of compounds in chemical reaction process usually.There is the variant of several metathesis reactions, such as ring-opening metathesis, acyclic dienes hydrocarbon transposition, ring closing metathesis and cross metathesis.

Produce the polyolefinic method multistep processes typically with terminal group functional group, the method usually produces refuse and the energy of undesired by product and reactant.

R.T.Mathers and G.W.CoatesChem.Commun.2004,422-423 page discloses the example using cross-metathesis, with the functionalized polyolefine hanging vinyl containing side, forms the polarity-functionalized products with grafting-type structure.

The people J.Am.Chem.Soc.2008 such as D.Astruc, the people Angew.Chem.Int.Ed.2005 such as 130, pp.1495-1506andD.Astruc, 44,7399-7404 page discloses the example using cross metathesis, with the functionalized non-polymer molecule containing vinyl.

About the summary forming the polyolefinic method of terminal group functional, see: (a) S.B.Amin and T.J.MarksAngew.Chem.Int.Ed.2008,47,2006-2025 page; (b) T.C.ChungProg.Polym.Sci.2002,27,39-85 page; (c) R.G.Lopez, F.DAgosto, C.BoissonProg.Polym.Sci.2007,32,419-454 page.

The USSN12/487739 that on June 19th, 2009 submits to discloses the oligopolymer and polymkeric substance that functionalised for some ethenyl blockings used in lubricant applications.

The USSN12/143663 submitted on June 20th, 2008 discloses oligopolymer and the polymkeric substance of some ethenyl blockings functionalized in the USSN12/487739 submitted on June 19th, 2009.

Extra interested reference comprises: U.S. Patent No. 4988764.

Therefore, metathesis reaction can provide the functionalised polyolefin with terminal group functional, but up to now, the functionalized polyolefine of polymerization end groups is infeasible on each other.

Therefore, need to prepare polyolefinic method, the method utilizes terminal group functional, provides the novel polymer with peculiar physical properties.

The triblock polymer prepared by polyolefinic many blocks of ethenyl blocking feature (a kind of undersaturated chemical reactivity internal site) by transposition in the application of wide region as expanding material, connecting layer properties-correcting agent, tensio-active agent and surface-modifying agent are interested.Hydrogenation causes unique triblock polymer, and described triblock polymer can use in such as those application described in unhydrided material.This document describes the polyolefinic many blocks by transposition ethenyl blocking, its novel production method.This method can be used for the polyolefine of a scope, comprising isotactic polyprophlene (iPP), and atactic polypropylene(APP) (aPP), ethylene propylene copolymer (EP) and polyethylene (PE).

Summary of the invention

The present invention relates to the composition containing the many block polyolefin represented with following formula:

PO-(-C=C-Z-) _n-C=C-PO* (I) or

PO-(-C-C-Z-) _n-C-C-PO*(Ia)

Wherein Z is a part for the cyclic monomer with at least one internal double bond, and this part retains after ring-opening metathesis reaction, preferred C ₁-C ₁₈alkyl or substituted hydrocarbon radical; PO and PO* is polyolefine, preferred PO and PO* independently of one another for having 9-10, the substituted or unsubstituted alkyl of 000 carbon atom; Be 1-about 10 with n, 000.The invention still further relates to the many block polyolefin represented with formula Ia be hydrogenated.

Describe in detail

Definition

Term as used herein " polyolefine " refers to the oligopolymer of two or more olefin monomer units or polymkeric substance and comprises particularly with undefined oligopolymer and polymkeric substance." alkene ", or be called " alkenes ", be there is the carbon of at least one double bond and the straight chain of hydrogen, side chain, or ring compound.Higher alkene is the alkene with a four or more carbon atom.Ethene should be regarded as alpha-olefin.

Propene polymer or oligopolymer contain at least 50mol% propylene, and ethene polymers or oligopolymer contain at least 50mol% ethene, and so on.

For the object of this specification sheets and claims, when polymkeric substance or multipolymer refer to containing alkene, comprising, but be not limited to, ethene, when propylene and butylene, the alkene existed in this polymkeric substance or multipolymer is the polymerized form of alkene.Such as, when it is said that multipolymer has " ethene " content of 35wt%-55wt%, be appreciated that as the monomeric unit in this multipolymer is derived from ethene in the polymerization, and described derivative unit exist, based on the weight of multipolymer with 35wt%-55wt%." polymkeric substance " has two or more identical or different monomeric units." homopolymer " is the polymkeric substance with identical monomeric unit." multipolymer " is the polymkeric substance with two or more monomeric units different from each other." ter-polymers " is the polymkeric substance with three monomeric units different from each other.Mention term that monomeric unit uses " difference " and show that monomeric unit differs at least one unit each other or isomery is different.Therefore, the definition of multipolymer used herein comprises ter-polymers and analogue.Oligopolymer has the polymkeric substance of lower molecular weight (Mn is less than 25,000g/mol, is preferably less than 2500g/mol) or low monomeric unit quantity (being such as less than or equal to 75 monomeric units) typically.

Mn used herein is that number-average molecular weight (is passed through ¹hNMR measures, except as otherwise noted), Mw is weight-average molecular weight (passing through gel permeation chromatography measurement), and Mz is z average molecular weight (passing through gel permeation chromatography measurement), wt% is weight percentage, and mol% is molecular fraction.Molecular weight distribution definition (MWD) (is passed through divided by Mn for Mw (passing through gel permeation chromatography measurement) ¹hNMR measures).Except as otherwise noted, the unit (such as, Mw, Mn, Mz) of all molecular weight is g/mol.

" allyl chain ends " is (also referred to as " vinyl ends ", " the vinyl end of the chain ", " allylic vinyl ends " or " contents of ethylene ") be defined as the polyolefine (oligopolymer or polymkeric substance) with at least one end group represented with formula I:

Wherein " " represents polyolefin chain.In preferred embodiments, allyl chain ends formula II represents:

Use ¹hNMR, at 120 DEG C, uses deuterate tetrachloroethane as solvent, on 500Hz machine, measures the content of allyl chain ends, and when selecting, pass through ¹³cNMR confirms.Resconi is at JAmericanChemicalSoc., 114,1992, the propylene oligomer for ethenyl blocking is reported in 1025-1032 page, the distribution of proton and carbon (mass spectrum uses pure perdeuterated tetrachloroethane, and carbon spectrum use just with the 50:50 mixture of perdeuterated tetrachloroethane; All spectrum, at 100 DEG C, for proton, under being 300MHz and for carbon, the BrukerAM300 spectrometer operated under 75.43MHz records), this is useful in this article.

" the isobutyl-end of the chain ", also referred to as " isobutyl-end group ", it is defined as the polyolefine (oligopolymer or polymkeric substance) with at least one end group represented with following formula:

Wherein M represents polyolefine (oligopolymer or polymkeric substance) chain.In preferred embodiments, isobutyl-chain one of following formula represents:

Wherein M represents polyolefin chain.

Use ¹³cNMR, with people such as Resconi, JAm.Chem.Soc., 1992,114, distribute (assignment) for 100% propylene oligomer (and polymkeric substance) and the chemical shift listed for E-P oligopolymer (and polymkeric substance) in Fig. 2 of WO2009/155471 in 1025-1032 page, measure isobutyl-end group % (as described in embodiment part).

The ratio of allylic vinyl " the isobutyl-end of the chain with " is defined as the ratio of isobutyl-end of the chain % and allylic vinyl %.

Except as otherwise noted, term " interior degree of unsaturation " refers to the double bond of non-allyl group chain defined above, vinylidene, or vinylidene base (vinylidene) degree of unsaturation.

Term " diblock " is defined as and refers to there are at least two polyolefine different pieces in many block polyolefin, and such as PO with PO* is different.Mention the term " difference " that polyolefine uses and show that polyolefinic monomeric unit differs at least one atom each other, polyolefinic monomeric unit isomery is different, or polyolefinic Mn, Mw, Mz, tacticity, Mw/Mn, g'vis, vinyl, vinylidene base, vinylidene, or interior degree of unsaturation content, co-monomer content (when comonomer is identical or different in polyolefine), density (ASTMD1505), fusing point, melting heat, Brookfield viscosity, proportion (ASTMD4052), or any other fluid or polyolefin properties are different, as US2008/0045638, described in paragraph [0593]-[0636] (when conflicting between the test procedure in this specification sheets and US2008/0045638, this specification sheets should account for leading).Term " many blocks " is defined as and refers to that being greater than a polyethylene fraction is present in many block polyolefin.Term " polyolefine of ethenyl blocking " is also referred to as " macromole of ethenyl blocking " or " VTM ", it is defined as has at least 30% allyl chain ends (relative to whole degree of unsaturation), preferred Mn is at least 300g/mol, the polyolefine of preferred 500-100,000g/mol.

As ChemicalandEngineeringNews, described in the 63 (5), the 27th page (1985), use the new labelling method of periodictable used herein.

Term " replacement " refers to that hydrogen base is by alkyl, heteroatoms or replace containing heteroatomic group.Such as, methyl cyclopentadiene (Cp) is by methyl substituted Cp base, and the ethyl that ethanol is replaced by-OH base.

Term " alkyl ", " hydrocarbyl group ", " group of hydrocarbon " is used interchangeably in this document.Equally, term " group " and " substituting group " are also used interchangeably in this document.For disclosure of the present invention, " alkyl " is defined as C ₁-C ₂₀group, it can be saturated or undersaturated, straight chain, side chain or ring-type (aromatics or non-aromatic), and comprises with undefined substituted hydrocarbon radical.

Substituted hydrocarbon radical be wherein at least one hydrogen atom by heteroatoms or containing heteroatomic group, preferably by least one functional group, such as halogen (Cl, Br, I, F), NR* ₂, OR*, SeR*, TeR*, PR* ₂, AsR* ₂, SbR* ₂, SR*, BR* ₂, SiR* ₃, GeR* ₃, SnR* ₃, PbR* ₃, and the group that similar group replaces, wherein at least one heteroatoms is inserted into alkyl inside, such as halogen (Cl, Br, I, F), O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR* ₂, GeR* ₂, SnR* ₂, PbR* ₂, and similar group, wherein R* is hydrogen or alkyl independently.

" substituted alkyl " or " substituted aryl " is the alkyl or aryl be made up of carbon and hydrogen, and wherein at least one hydrogen is by heteroatoms, containing heteroatomic group, or has the straight chain of 1-30 carbon atom, side chain, or the substituted or unsubstituted alkyl of ring-type replaces.

" reactive terminal group " refers to have vinyl, vinylidene base, vinylidene or can be grouped to the polymkeric substance of other end groups of polymer chain of growth.

Following abbreviation can be used in whole specification sheets.Me is methyl, and Ph is phenyl, and Et is ethyl, and Pr is propyl group, iPr is sec.-propyl, and n-Pr is n-propyl, and Bu is butyl, and iBu is isobutyl-, tBu is the tertiary butyl, and p-tBu is the p-tertiary butyl, and nBu is normal-butyl, and TMS is trimethyl silyl, TIBAL is triisobutyl aluminium, and TNOAL is triisobutyl octyl aluminum, and MAO is methylaluminoxane, pMe is p-methyl, and Ar* is 2,6-di-isopropyl aryl, Bz is benzyl, and THF is tetrahydrofuran (THF), and RT is room temperature and tol is toluene.

Many block polyolefin

The present invention relates to the method for many block polyolefin and the many block polyolefin of preparation represented with following formula:

PO-(-C=C-Z-) _n-C=C-PO* (I) or

PO-(-C-C-Z-) _n-C-C-PO*(Ia)

Wherein Z is a part for the cyclic monomer with at least one internal double bond, and this part retains after ring-opening metathesis reaction, and preferred Z is C ₁-C ₁₈alkyl or substituted hydrocarbon radical (comprising alkene and substituted olefine), preferred C ₁-C ₁₂alkyl or substituted hydrocarbon radical, preferred C ₁-C ₁₀(substituting group preferably on substituted hydrocarbon radical is C for alkyl or substituted hydrocarbon radical ₁-C ₅alkyl or C ₁-C ₅substituted hydrocarbon radical) (such as, methyl, ethyl, propyl group, butyl, amyl group or its isomer), halogen (such as, Br, Cl, I or F), (such as, alkyl oxide, alkyl ester, aryl ethers or aryl ester, wherein alkyl is C for ether or ester ₁-C ₂₀alkyl, and aryl is C ₆-C ₂₀aryl, preferable methyl ether, ethyl ether, methyl ethyl ether, butyl ether, propyl ether, and analogue), ketone, nitric ether (nitrate) or hydroxyl;

PO and PO* is polyolefine, preferred PO and PO* is independently of one another for having 9-10,000 carbon atom (preferred 20-7500 carbon atom, preferred 30-4000, preferred 40-2000) substituted or unsubstituted alkyl, at least one in preferred PO and PO* has 20-10,000 carbon atom, preferred 30-2000; With

N is 1-about 10,000, especially about 10-about 7500, more specifically about 50-about 5000, and in an aspect, is about 100-about 2000.

For the polyolefine of many blocks of formula (I), preferred embodiment has different PO and PO*.Its example is PO is isotactic PP, and PO* is EP multipolymer, and the ethylene content in PO* is about 50wt%.For many block polyolefin of formula (X), preferred embodiment has different PO and PO*, and PO and PO* unmixing.If blended together with the polyolefine that unmixing refers to the ethenyl blocking becoming PO with PO*, then they will form heterogeneous composition.

Uniform composition refers to the composition with a pattern phase substantially.(for the present invention and appended claim, altogether-continuous print pattern is regarded as single state).Such as, wherein the blend of two kinds of polymkeric substance of a kind of polymkeric substance and another Polymers Miscibility is considered to solid homogenous.Use opticmicroscope, scanning electron microscope (SEM) or atomic force microscope (AFM), measure this pattern, when opticmicroscope, SEM and AFM provides different data, then should use SEM data.On the contrary, for immiscible blend, observe two independently phases.Miscible blend is uniform, and immiscible blend is heterogeneous.

In preferred embodiments, for many block polyolefin of formula (I) or formula (Ia), PO and PO* comprises about 15wt%-and is about 95wt% ethene and has and be greater than 80% allyl chain ends (relative to whole degree of unsaturation).

In preferred embodiments, for many block polyolefin of formula (I) or formula (Ia), PO and PO* comprises about 30wt%-and is about 95wt% ethene and has and be greater than 70% allyl chain ends (relative to whole degree of unsaturation).

In preferred embodiments, for many block polyolefin of formula (I) or formula (Ia), PO and PO* comprises about 30wt%-and is about 95wt% ethene and has and be greater than 90% allyl chain ends (relative to whole degree of unsaturation).

In preferred embodiments, for many block polyolefin of formula (I) or formula (Ia), PO and PO* comprises about 15wt%-and is about 95wt% propylene and has and be greater than 80% allyl chain ends (relative to whole degree of unsaturation).

In preferred embodiments, for many block polyolefin of formula (I) or formula (Ia), PO and PO* comprises about 30wt%-and is about 95wt% propylene and has and be greater than 70% allyl chain ends (relative to whole degree of unsaturation).

In preferred embodiments, for many block polyolefin of formula (I) or formula (Ia), PO and PO* comprises about 30wt%-and is about 95wt% propylene and has and be greater than 90% allyl chain ends (relative to whole degree of unsaturation).

In preferred embodiments, for many block polyolefin of formula (I) or formula (Ia), PO and PO* comprises about 15wt%-and is about 95wt% ethylene-propylene copolymer and has and be greater than 80% allyl chain ends (relative to whole degree of unsaturation).

In preferred embodiments, for many block polyolefin of formula (I) or formula (Ia), PO and PO* comprises about 30wt%-and is about 95wt% ethylene-propylene copolymer and has and be greater than 70% allyl chain ends (relative to whole degree of unsaturation).

In preferred embodiments, for many block polyolefin of formula (I) or formula (Ia), PO and PO* comprises about 30wt%-and is about 95wt% ethylene-propylene copolymer and has and be greater than 90% allyl chain ends (relative to whole degree of unsaturation).

In some embodiments, for passing through ¹the Mn that HNMR measures is the multi-block polymer of maximum 60,000g/mol, and many block polyolefin have unsaturated site/polyolefin chain in average about 0.75-about 4.0, and this is by polyolefinic ¹hNMR measures.Preferably, many block polyolefin are hydrogenated, and for passing through ¹the Mn that HNMR measures is the multi-block polymer of maximum 60,000g/mol, and many block polyolefin on average have and are less than unsaturated site/polyolefin chain in 1.25, and this is by polyolefinic ¹hNMR measures.

In preferred embodiments, PO* is PO and/or PO is PO*.In another preferred embodiment, many block polyolefin are polyolefine, and this polyolefine is the mixture of at least three kinds of forms of formula I, and such as many block polyolefin can be following mixtures:

PO-(-C=C-Z-) _n-C=C-PO*(I)，

PO-(-C=C-Z-) _n-C=C-PO (II), or

PO*-(-C=C-Z-) _n-C=C-PO*(III)

Wherein Z, PO, PO* and n are described above.As mentioned above, PO and PO* can be identical or different.Preferably, the mixture of I, II and III comprises many block polyolefin (I) of about 30%-about 70%, many block polyolefin (II) of about 1%-about 30%, and many block polyolefin (III) of about 1%-about 30%.

In another preferred embodiment, many block polyolefin are polyolefine, and this polyolefine is the mixture of at least three kinds of forms of formula Ia, and such as many block polyolefin can be following mixtures:

PO-(-C-C-Z-) _n-C-C-PO*(Ia)

PO-(-C-C-Z-) _n-C-C-PO(IIa)

PO*-(-C-C-Z-) _n-C-C-PO*(IIIa)。

Preferably, the mixture of Ia, IIa and IIIa comprises many block polyolefin (Ia) of about 30%-about 70%, many block polyolefin (IIa) of about 1%-about 30%, and many block polyolefin (IIIa) of about 1%-about 30%, wherein Z, PO, PO* and n are described above.As mentioned above, PO and PO* can be identical or different.

Use preparative classification, by dissolve or Tc (it comprises preparative Rising Elution Fractionation (Prep-TREF) and methods involving (such as, use the PREP-mc2 instrument available from PolymerChAR, with TREF or CRYSTAF pattern)), many block polyolefin mixture of I, II and III or Ia, IIa and IIIa can be classified into three independently component I, II and III or Ia, IIa or IIIa.If the Mn of PO and PO* is significantly different, then by preparative classification, by molecular weight, (it comprises the extraction of use solvent-nonsolvent or intermediate processing (such as, uses the PREP-mc2 instrument available from PolymerChAR, with MW pattern)), be separated these three independent components.

As use TREF, when many block polyolefin mixture is fractionated into three cuts, the number-average molecular weight (Mn) of the part of middle degree of crystallinity (crystallinity) (this is measured by the gel permeation chromatography (GPC-3D) with triple (triple)-detector) is also in each the centre of Mn of other two parts.When each the eluting temperature of eluting temperature and other two parts of the part of middle degree of crystallinity differs at least 5 DEG C, especially about 10 DEG C, more specifically 20 DEG C time, typical separation can be realized.

In an alternative embodiment, can the various components (such as, following preparative TREF operation can be used, (I) and (II) and (III) are separated) of many block polyolefin separated from one another.In preferred embodiments, once the many block polyolefin of classification, then select the part (and think produce many block polyolefin) containing the biggest quality herein, and characterize, such as DSC (as described below).Preferably, many block polyolefin (such as having the part of the selection of the biggest quality) demonstrate two or more peak melt temperature (Tm) according to DSC, preferably three Tm, and Tm differs at least 5 DEG C each other, preferred difference at least 10 DEG C, preferred difference at least 20 DEG C, preferably difference at least 30 DEG C, preferably difference at least 40 DEG C, preferred difference at least 50 DEG C, preferred difference at least 60 DEG C, preferably difference at least 70 DEG C, preferably difference at least 80 DEG C.

Equally, preferably, many block polyolefin (such as, there is the part of the selection of the biggest quality) demonstrate at least two Tcs (Tc) according to DSC, preferably three Tc, and Tc differs at least 5 DEG C each other, preferred difference at least 10 DEG C, preferred difference at least 20 DEG C, preferably difference at least 30 DEG C, preferably difference at least 40 DEG C, preferred difference at least 50 DEG C, preferred difference at least 60 DEG C, preferably difference at least 70 DEG C, preferably difference at least 80 DEG C.

Further, in preferred embodiments, the melting heat (Hf) of many block polyolefin (such as, having the part of the selection of the biggest quality) measured according to DSC is between the polyolefinic Hf of initial dimerization.Preferably, many block polyolefin (such as, there is the part of the selection of the biggest quality) melting heat (Hf) differ with the polyolefinic Hf of initial dimerization at least 5J/g (if when using two or more dimers, then use the dimeric Hf with the highest Hf), preferred difference at least 10J/g, preferred difference at least 20J/g, preferably differs at least 50J/g, preferably differs at least 80J/g.

In preferred embodiments, the Hf at least 5J/g fewer than the polyolefinic Hf of the initial dimerization with the highest Hf of many block polyolefin (such as, there is the part of the selection of the biggest quality), preferably few at least 10J/g, preferably few at least 20J/g, preferably few at least 30J/g, preferably few at least 40J/g, preferably few at least 50J/g, preferably few at least 60J/g, preferably few at least 70J/g, preferably few at least 80J/g, preferably few at least 90J/g.

In another embodiment, many block polyolefin (such as, there is the part of the selection of the biggest quality) in the content of comonomer and the polyolefine of initial dimerization the content of comonomer differ at least 5mol% (if when there are two or more dimers, then for this comparatively, use the dimer with most high comonomer content), preferably differ at least 10mol%, preferably differ at least 20mol%, preferred difference at least 30mol%, preferably differs at least 40mol%.Homopolymer should be regarded as having 0mol% comonomer.By the sample that fourier transform infrared spectroscopy (FTIR) is collected in combination with GPC, measure co-monomer content, as Wheeler and Willis at AppliedSpectroscopy, the 1993,47th volume, described in 1128-1130 page.

Use business preparative TREF instrument (ModelMC2, PolymerChar.S.A.), fractionation of resins is become chemical composition cut.About 2g polymkeric substance is placed in reactor, and is dissolved in 200ml dimethylbenzene, stablize about 60 minutes with 600ppmBHT at 130 DEG C.Make this mixture stablize 45 minutes at 90 DEG C, then use the speed of cooling of 0.1 DEG C/min, be cooled to or 30 DEG C (standard procedure) or 15 DEG C (Cryo operation).Raise the temperature of mixture of cooling, until it is within the scope of used minimum separation temperature (see table 2), and heat this mixture, maintain its temperature in specialized range 20 minutes.Mixture is filtered through according to the order of sequence the pillar strainer of 75 microns, then uses the pressurized nitrogen of 10psi-50psi, by the disk filter of 2 microns.By 50ml dimethylbenzene washing reactor 2 times, wherein heat described dimethylbenzene, to maintain the temperature of purging compound in the temperature range of indication, and in each cycles of washing process, keep 20 minutes at such a temperature.By introducing fresh dimethylbenzene (200ml dimethylbenzene, stablize with 600ppmBHT) in reactor, raise the temperature of this mixture, until it reaches the maximum separation temperature scope of the shown next one sequentially of table 2, and heat this mixture, to maintain its temperature in specialized range 20 minutes, filter as mentioned above afterwards, thus continue grading technology.Repeatedly extract circulation according to the order of sequence in such a way, until be extracted this mixture within the scope of all separation temperatures shown in table 2.Extract degree uses methanol extraction independently, to reclaim independent polymer moieties.

Table 2

* for standard procedure, separation temperature scope is 0-36 DEG C.

In preferred embodiments, the Mn of many block polyolefin is maximum 200,000g/mol, preferred 400-12,000g/mol, preferred 1000-about 60,000g/mol, preferably 10,000-45,000g/mol, preferably 20,000-42,000g/mol, preferably about 40,000g/mol, or about 20,000 or about 1000g/mol.

In one embodiment, the Mn of PO is greater than 300, preferred 400-120, and 000, preferred 500-100,000, preferred 600-60,000g/mol.

In one embodiment, PO, and the polypropylene of optionally PO* to be Mn be about 300-about 20,000g/mol, or the ethylene/propene copolymer of PO to be Mn be about 300-about 20,000g/mol.In preferred embodiments, at least one the substituted or unsubstituted alkyl in PO and PO* is containing 2-about 18 carbon atoms of having an appointment.In preferred embodiments, PO is stereospecific, preferred isotaxy, or syndyotactic.PO and PO* be particularly useful can be isotaxy, height isotaxy, syndiotaxy, or highly syndyotactic propene polymer, especially isotactic polyprophlene." isotaxy " used herein is defined as the isotaxy five unit group with at least 10%, preferably basis ¹³c-NMR analyzes, and has at least 40% by the isotaxy five unit group of the methyl of propylene derived." height isotaxy " used herein is defined as basis ¹³c-NMR analyzes, and has the isotaxy five unit group of at least 60%.In required embodiment, PO, and/or PO* and/or produce the degree of isotacticity that the polyolefine of ethenyl blocking that PO and PO* use has at least 85%." syndiotaxy " used herein is defined as basis ¹³c-NMR analyzes, and has at least 10% syndyotactic five unit groups, and preferably at least 40%." height syndiotaxy " used herein is defined as basis ¹³c-NMR analyzes, and has the syndiotaxy five unit group of at least 60%.In another embodiment, PO, and/or PO* and/or produce the degree of syndiotacticity that the polyolefine of ethenyl blocking that PO and PO* use has at least 85%.

In one embodiment, the polypropylene of PO to be Mn be about 300-about 20,000g/mol, and PO* is not polypropylene.

It is considered herein that PO and PO* is derived from the polyolefinic dimer manufacturing the one or more of ethenyl blockings that dimer uses, described dimer is for the manufacture of many block polyolefin.

In another embodiment, many block polyolefin are liquid at 25 DEG C.In another embodiment, the viscosity index (ASTM2270) of many block polyolefin is more than or equal to 120, or is more than or equal to 130, or be more than or equal to 150, or be more than or equal to 200, or be more than or equal to 250, or be more than or equal to 300.

In another embodiment, the viscosity of many block polyolefin described herein at 60 DEG C is greater than 1000cP, is greater than 12,000cP, or is greater than 100,000cP.In other embodiments, the viscosity of many block polyolefin is less than 200,000cP, is less than 150,000cP, or is less than 100,000cP.Use Brookfield Digital Viscometer, measure viscosity.

In another embodiment, PO and PO* one or both of is not poly-aromatic monomer material, such as polystyrene.Equally, preferred PO and PO* comprises and is less than 0.1wt% aromatic monomer, such as vinyl-arene, such as vinylbenzene or derivatives thereof.Equally, in preferred embodiments, "-(-C=C-Z-) _n-" not polyvinyl arene, such as vinylbenzene or derivatives thereof.In preferred embodiments, the many block polyolefin produced herein comprise and are less than 0.1wt% aromatic monomer (such as vinylbenzene), preferred 0wt%.

Typical condition can be used, catalytic hydrogenation contains polyolefine many blocks product of interior degree of unsaturation, such as use formula I, II or III describe those, obtain interested completely saturated polyolefin products, this is because they have undesired oxidation and other chemical reactions, the stability of increase causes.In the molten state, in the solution, or as slurry, at 0.01-100MPa hydrogen and suitable hydrogenation catalyst, such as, under the loaded metal existence of 8-10 race, hydrogenation can be carried out.

In another embodiment, hydrogenatable any many block polyolefin described herein.Especially, optionally process many block polyolefin, reduce and contain heteroatomic compound to being less than 600ppm, then contact with hydrogenation catalyst with hydrogen, produce many block polyolefin that bromine number is less than 1.8.In preferred embodiments, the many block polyolefin processed comprise and are less than or equal to 100ppm containing heteroatomic compound, are preferably less than or equal to 50ppm containing heteroatomic compound.(being the compound of at least one atom contained in addition to carbon and hydrogen containing heteroatomic compound).Preferably, hydrogenation catalyst is selected from the 7th of load the, and 8,9 and 10 race's metals, preferably in silicon oxide, aluminum oxide, clay, titanium oxide, zirconium white or mixed-metal oxide support load be selected from Ni, Pd, Pt, Co, Rh ,-74-Fe, Ru, the one or more of hydrogenation catalysts of Os, Cr, Mo and W.Preferred hydrogenation catalyst is the nickel of load over celite, or the platinum of load on alumina or palladium, or the cobalt-molybdenum of load on alumina.The catalyzer of usual use high nickel content, such as on diatomite catalyzer 60% Ni, or there is the supported catalyst of high-content Co-Mo load.Or hydrogenation catalyst is at diatomite, silicon oxide, aluminum oxide, the nickel of load on clay or silica-alumina.

In preferred embodiments, many block polyolefin and hydrogen and hydrogenation catalyst, at 25-350 DEG C, contact at the temperature of preferred 100-300 DEG C.In another preferred embodiment, many block polyolefin contact 5 minutes-100 hours with hydrogen with hydrogenation catalyst, preferably the time period of 5 minutes-24 hours.In another preferred embodiment, many block polyolefin and hydrogen and hydrogenation catalyst, at 25psi-2500psi, contact under the hydrogen pressure of preferred 100-2000psi.Can in slurry-phase reactor, with periodical operation, or in continuous agitator tank reactor (CSTR), wherein by the catalyzer of the 0.001wt%-20wt% of many block polyolefin raw material or preferred 0.01-10wt%, hydrogen and many block polyolefin join in reactor continuously, allow certain residence time, usual 5 minutes-10 hours, make the complete hydrogenation of unsaturated olefin, thus realize this hydrogenation process.The catalytic amount added is usually very little, the only inactivation of compensate for catalyst.Many block polyolefin of catalyzer and hydrogenation are drawn continuously from reactor.Then this product mixtures is filtered, centrifugal or sedimentation, to remove solid hydrogenation catalyst.Regenrable catalyzed dose and recycle.Many block polyolefin of hydrogenation former state can use or distill further.

In another embodiment, the any many block polyolefin produced herein are hydrogenated, and bromine number is less than or equal to 1.8, this is by ASTMD1159 (or ASTM2710, if ASTMD1159 so guides) measure, preferably be less than or equal to 1.7, preferably be less than or equal to 1.6, be preferably less than or equal to 1.5, be preferably less than or equal to 1.4, preferably be less than or equal to 1.3, preferably be less than or equal to 1.2, be preferably less than or equal to 1.1, be preferably less than or equal to 1.0, preferably be less than or equal to 0.5, be preferably less than or equal to 0.1.

The many block polyolefin produced can be used herein in the application of wide region, such as expanding material, connecting layer properties-correcting agent, tensio-active agent, surface-modifying agent, lubricant, washing composition, flocculation agent, viscosity modifier, VI improver, emulsifying agent, emulsion splitter, dispersion agent, softening agent, for the tensio-active agent of soap class, washing composition, fabric softener, static inhibitor, oil additive, antifog or wetting additive, adhesion promotor, tackiness agent, for the additive of lubricant and/or fuel, thermoplastic elastomer, thermoplastics, elastomerics, and analogue.

In some embodiments, can at the goods of blend and manufacture, such as film, fiber, supatex fabric, or moulded parts (injection moulding and/or blowing), such as US2004/0106723 paragraph [0197-0257] in describe those in use the many block polyolefin produced herein.

Prepare the method for many block polyolefin

The present invention also provides the appropriate method of many block polyolefin of preparation formula (I), the method comprises makes olefin metathesis catalyst, contact with the polyolefinic dimer (VTP) of ethenyl blocking with containing the cyclic hydrocarbon group monomer of at least one internal double bond, wherein the polyolefine of each ethenyl blocking has the allyl chain ends of at least 30%, relative to whole degree of unsaturation (preferably at least 40%, preferred at least 50%, preferred at least 60%, preferred at least 65%, preferably at least 75%, preferably at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95%).This dimer can be the dimer of identical VTP or can be 2,3,4 or more the dimers of planting VTP, the preferably dimer of one or both VTP.Such as, if use two kinds of VTP (A and B), then this dimer can be A-A, A-B, B-B; If or using three kinds of dimer VTP (A, B and C), then this dimer can be A-A, A-B, A-C, B-B, B-C, C-C; If or using four kinds of dimer VTP (A, B, C and D), then this dimer can be A-A, A-B, A-C, A-D, B-B, B-C, B-D, C-C, C-D, D-D etc.

Typically in reaction vessel, at the temperature of 20-200 DEG C (preferred 50-160 DEG C, preferred 60-140 DEG C) under and pressure (the preferred 0.5-500MPa of 1Pa-1000MPa, preferred 1-250MPa) under combine reactants (comprising the polyolefinic dimer of ethenyl blocking, such as PO and PO* is by its derivative dimer) residence time of 0.5 second-10 hours (preferably 1 second-5 hours, preferably 1 minute-1 hour).

Typically, relative to the every mol dimer introduced, by 0.00001-0.1mol, preferred 0.0001-0.02mol, preferred 0.0005-0.01mol catalyzer is incorporated in reactor.In some embodiments of the present invention, relative to the dimer that every mol introduces, by about 0.7-about 4.0 (such as 0.8-2.6), preferably about 1.0-about 2.0, and most preferably from about 1.1-is about 1.7mol and is incorporated in reactor containing the cyclic hydrocarbon group monomer of at least 1 internal double bond.Or, the mole number of cyclic hydrocarbon monomer and the ratio >1:1 of the dimeric mole number be incorporated in reactor, preferred 50:1, preferred 100:1, preferred 200:1.

The method typically is solution method, although it can be body or high-pressure process.Preferred homogeneous method.(homogeneous method is defined as the method that wherein at least 90wt% product is solvable in reaction medium.) especially preferred body homogeneous method.(concentration that substance law is defined as reactant in all raw materials wherein in reactor is more than or equal to the method for 70 volume %.) or there is not solvent or thinner, or do not have solvent or thinner to join in reaction medium, (exception be the carrier being used as in a small amount catalyzer or other additives, or typically find the consumption together with reactant, such as, propane in propylene).

Suitable diluent/solvent for the method comprises the inert liq of non-coordination.Example comprises straight chain and branched-chain hydrocarbon, such as Trimethylmethane, butane, pentane, iso-pentane, hexane, isohexane, heptane, octane, dodecane, and composition thereof; Ring-type and clicyclic hydrocarbon, such as hexanaphthene, suberane, methylcyclohexane, methylcycloheptane, and composition thereof, such as commercial those (Isopar findable ^tM); Perhalogenation hydrocarbon, such as perfluorination C _4-10alkane, chlorobenzene, and the aromatic substance of aromatics and alkyl replacement, such as benzene, toluene, 1，3，5-trimethyl-benzene and dimethylbenzene.In preferred embodiments, preferred aliphatic series hydrocarbon solvent, such as Trimethylmethane, butane, pentane, iso-pentane, hexane, isohexane, heptane, octane, dodecane, and composition thereof; Ring-type and clicyclic hydrocarbon, such as hexanaphthene, suberane, methylcyclohexane, methylcycloheptane, and composition thereof.In another embodiment, solvent is not aromatic hydrocarbons, and the amount of preferred aromatic hydrocarbons in solvent is less than 1wt%, preferred 0.5wt%, preferred 0wt%, based on the weight of solvent.

In another embodiment, the method is slurry process.Term as used herein " slurry polymerization process " refers to the polymerization process that the catalyzer of wherein working load and monomer are polymerized on the granules of catalyst of load.The polymer product that at least 95wt% is derived by the catalyzer of load is the particle form (not being dissolved in thinner) as solid particulate.

In preferred embodiments, for the material concentration of the method for being less than or equal to 60 volume % solvents, being preferably less than or equal to 40 volume % solvents, being preferably less than or equal to 20 volume % solvents.

The method can be interval, semi-batch or continuous processing.Term as used herein refers to the system operated when not having interference or interrupting continuously.Such as, the continuous processing of producing polymkeric substance is the method that wherein reactant is incorporated in one or more reactor continuously and polymer product is drawn continuously.

Useful reaction vessel comprises reactor (comprising continuous agitator tank reactor, batch reactor, reactive extruder, pipeline or pump).

In preferred embodiments, the productivity of the method be the many block polyolefin/mmol catalyzer of at least 200g formula (I)/hour, preferably at least 5000g/mmol/h, preferably at least 10,000g/mmol/h, preferably at least 300,000g/mmol/h.

" reaction zone ", also referred to as " polymeric area ", it is defined as the catalyzer wherein activated and contacts with monomer and the region of polymerization reaction take place.When with or series connection or parallel-connection structure use multiple reactor time, each reactor is regarded as independently polymeric area.For the multi-stage polymeric in both batch reactor and flow reactor, each polymeric segment is regarded as independently polymeric area.Room temperature is 23 DEG C, except as otherwise noted.

The invention further relates to a kind of many block polyolefin method of production formula (I), preferred on-line method, preferred continuous processing, the method comprises and is incorporated in reactor by monomer and catalyst system, obtain the polyolefinic reactor effluent containing ethenyl blocking, optionally remove (such as flashing away) solvent, untapped monomer and/or other volatile matters, obtain the polyolefine of two kinds of ethenyl blockings (such as, described herein those), the polyolefine of ethenyl blocking and olefin metathesis catalyst are incorporated in reaction zone, obtain the polyolefinic dimer of ethenyl blocking, by described dimer, cyclic monomer and the olefin metathesis catalyst with at least one degree of unsaturation are incorporated into reaction zone (such as reactor, forcing machine, pipeline and/or pump) in, and the many block polyolefin obtaining formula (I) (such as, described herein those), many block polyolefin of optionally hydrogenation of formula (I) afterwards, obtain many block polyolefin of formula (Ia).

Olefin metathesis catalyst

Olefin metathesis catalyst described herein is the following compound of catalysis: the reaction 1) between the polyolefine of the first ethenyl blocking and the polyolefine of the second ethenyl blocking, when typically eliminating ethene, produces dimer; Or 2) reaction between dimer and the cyclic monomer with at least one degree of unsaturation, to produce many block polyolefin described herein.

In preferred embodiments, olefin metathesis catalyst is represented by formula (IA):

Wherein:

M is the 8th race's metal, preferred Ru or Os, preferred Ru;

X and X ¹be any anion ligand independently, preferred halogen (preferred Cl), alkoxyl group or trifluoromethanesulfonic acid root; Or X and X ¹in conjunction with formation two anionic group, and can form the monocycle of maximum 30 non-hydrogen atoms or the polycyclic ring system of maximum 30 non-hydrogen atoms;

L and L ¹be two neutral electron donors independently, preferred phosphine or N-heterocycle carbine, L and L ¹can in conjunction with the formation monocycle of maximum 30 non-hydrogen atoms or the polycyclic ring system of maximum 30 non-hydrogen atoms;

L and X in conjunction with the multiple tooth monoanionic group of formation, and can form the monocycle of maximum 30 non-hydrogen atoms or the polycyclic ring system of maximum 30 non-hydrogen atoms;

L ¹and X ¹in conjunction with the multiple tooth monoanionic group of formation, and can form the monocycle of maximum 30 non-hydrogen atoms or the polycyclic ring system of maximum 30 non-hydrogen atoms;

R and R ¹be hydrogen or C independently ₁-C ₃₀substituted or unsubstituted alkyl (preferred C ₁-C ₃₀substituted or unsubstituted alkyl or substituted or unsubstituted C ₄-C ₃₀aryl);

R ¹and L ¹or X ¹can in conjunction with the formation monocycle of maximum 30 non-hydrogen atoms or the polycyclic ring system of maximum 30 non-hydrogen atoms;

R and L or X can in conjunction with the formation monocycle of maximum 30 non-hydrogen atoms or the polycyclic ring system of maximum 30 non-hydrogen atoms.

Preferred alkoxyl group comprises those, and wherein alkyl is phenol, and (wherein phenol can by maximum 1,2,3,4 or 5 C for fortified phenol ₁-C ₁₂alkyl replaces) or C ₁-C ₁₀alkyl, preferred C ₁-C ₁₀alkyl, preferable methyl, ethyl, propyl group, butyl or phenyl.

Preferred trifluoromethanesulfonic acid root formula (IIA) represents:

Wherein R ²hydrogen or C ₁-C ₃₀alkyl, preferred C ₁-C ₁₂alkyl, preferable methyl, ethyl, propyl group, butyl or phenyl.

Preferred N-heterocycle carbine formula (IIIA) or formula (IVA) represent:

Wherein:

Each R ⁴independently for there is alkyl or the substituted hydrocarbon radical of 1-40 carbon atom, preferable methyl, ethyl, propyl group, butyl (comprising isobutyl-and normal-butyl), amyl group, cyclopentyl, hexyl, cyclohexyl, octyl group, ring octyl group, nonyl, decyl, ring decyl, dodecyl, cyclo-dodecyl, 1，3，5-trimethyl-benzene base, adamantyl, phenyl, benzyl, tolyl, chloro-phenyl-, phenol, fortified phenol, or CH ₂c (CH ₃) ₃; With

Each R ⁵for hydrogen, halogen, or C ₁-C ₁₂alkyl, preferred hydrogen, bromine, chlorine, methyl, ethyl, propyl group, butyl or phenyl.

In the embodiment that other are useful, in formula (IIIA) or formula (IVA), be bonded to one of N base on Cabbeen S, O or P atom, preferred S atom replaces.

Other useful N-heterocycle carbines are included in Hermann, W.A.Chem.Eur.J.1996,2, pp.772 and 1627; The people such as Enders, D., Angew.Chem.Int.Ed.1995, the 34,1021st page; AlderR.W., Angew.Chem.Int.Ed.1996, the 35,1121st page; And the people such as Bertrand, G., Chem.Rev.2000, describe in the 100,39th page those.

In preferred embodiments, olefin metathesis catalyst be following in one or more of: tricyclohexyl phosphine [1, 3-two (2, 4, 6-trimethylphenyl) imidazoles-2-subunit] [3-phenyl-1H-indenes-1-subunit] ruthenous chloride (II), tricyclohexyl phosphine [3-phenyl-1H-indenes-1-subunit] [1, 3-two (2, 4, 6-trimethylphenyl)-4, 5-dihydro-imidazol--2-subunit] ruthenous chloride (II), tricyclohexyl phosphine [1, 3-two (2, 4, 6-trimethylphenyl)-4, 5-dihydro-imidazol--2-subunit] (thiophenyl) methylene radical] ruthenous chloride (II), two (tricyclohexyl phosphine)-3-phenyl-1H-indenes-1-subunit ruthenous chloride (II), 1, 3-two (2, 4, 6-trimethylphenyl)-4, 5-glyoxalidine-2-subunit [2-(isopropoxy)-5-(N, N-dimethylamino-sulfonyl) phenyl] methylene chloride ruthenium (II), [1, 3-two (2, 4, 6-trimethylphenyl)-2-imidazolidine subunit]-[2-[[(4-aminomethyl phenyl) imino-] methyl]-4-oil of mirbane phenolic group]-[3-phenyl-1H-indenes-1-subunit] ruthenous chloride (II).

In another embodiment, olefin metathesis catalyst above formula (IA) represents, wherein M is Os or Ru; R ¹hydrogen; X and X ¹can be identical or different, and be any anion ligand; L and L ¹can be identical or different, and be the electron donor of any neutrality; Can be hydrogen with R, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl.R is preferably hydrogen, C ₁-C ₂₀alkyl, or aryl.C ₁-C ₂₀alkyl can optionally by one or more aryl, halogen root, hydroxyl, C ₁-C ₂₀alkoxyl group or C ₂-C ₂₀alkoxy carbonyl replaces.Aryl is optionally by one or more C ₁-C ₂₀alkyl, aryl, hydroxyl, C ₁-C ₅alkoxyl group, amino, nitro or halogen foundation group replace.L and L ¹preferably chemical formula is PR ^{3 '}r ^{4 '}r ^{5 '}phosphine, wherein R ^{3 '}secondary alkyl or cycloalkyl, and R ^{4 '}and R ^{5 '}aryl, C ₁-C ₁₀primary alkyl, secondary alkyl, or cycloalkyl.R ^{4 '}and R ^{5 '}can be identical or different.L and L ¹preferably identical, and be-P (cyclohexyl) ₃,-P (cyclopentyl) ₃, or-P (sec.-propyl) ₃.X and X ¹be most preferably identical and be chlorine.

In another embodiment of the present invention, ruthenium and osmium carbene compound have formula (V):

Wherein M is Os or Ru, preferred Ru; X,X ¹, L and L ¹as mentioned above; And R ⁹and R ¹⁰can be identical or different and can be hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl.R ⁹and R ¹⁰base optionally comprises one or more following functional group: alcohol, mercaptan, ketone, aldehyde, ester, ether, amine, imines, amino, nitro, carboxylic acid, disulfide, carbonic ether, isocyanic ester, carbon imide, hydrocarbon alkoxyl group (carboalkoxy), and halogen group.These compounds and synthesis thereof are disclosed in U.S. Patent No. 6111121.

In another embodiment, useful olefin metathesis catalyst can be at United States Patent(USP) Nos. 6 herein, 111,121, 5,312,940, 5,342,909, 7,329,758, 5,831,108, 5,969,170, 6,759,537, 6,921,735, the any one catalyzer described in No.2005-0261451A1 is announced with the U.S.: comprising, but be not limited to, benzal base-bis-(tricyclohexyl phosphine) dichloro closes ruthenium, benzal base [1, 3-two (2, 4, 6-trimethylphenyl)-2-imidazoles alkylidene] dichloro (tricyclohexyl phosphine) ruthenium, dichloro (adjacent isopropoxy benzene methylene) (tricyclohexyl phosphine) ruthenium (II), (1, 3-two-(2, 4, 6-trimethylphenyl)-2-imidazoles alkylidene) dichloro (adjacent isopropoxy benzene methylene) ruthenium, 1, 3-pair-(2-aminomethyl phenyl)-2-imidazoles alkylidene] dichloro (2-isopropoxy benzene methylene) ruthenium (II), [1, 3-two (2, 4, 6-trimethylphenyl)-2-imidazoles alkylidene] dichloro [3-(2-pyridyl) propylidene base] ruthenium (II), [1, two (2-the aminomethyl phenyl)-2-imidazoles alkylidene of 3-] dichloro (phenylmethylene) (tricyclohexyl phosphine) ruthenium (II), [1, 3-two (2, 4, 6-trimethylphenyl)-2-imidazoles alkylidene] dichloro (3-methyl-2-fourth fork base) (tricyclohexyl phosphine) ruthenium (II), [1, 3-two (2, 4, 6-trimethylphenyl)-2-imidazoles alkylidene] dichloro (benzal base) two (3-bromopyridine) ruthenium (II).

In another embodiment, olefin metathesis catalyst following formula represents:

Wherein:

M* is the 8th race's metal, preferred Ru or Os, preferred Ru;

X* and X ^1*be any anion ligand independently, preferred halogen (preferred Cl), alkoxyl group or alkylsulfonate, or X and X ¹can be in conjunction with, form two anionic groups, and the monocycle of maximum 30 non-hydrogen atoms or the polycyclic ring system of maximum 30 non-hydrogen atoms can be formed;

L* is N, O, P or S, preferred N or O;

R* is hydrogen or C ₁-C ₃₀alkyl or substituted hydrocarbon radical, preferable methyl;

R ¹*, R ²*, R ³*, R ⁴*, R ⁵*, R ⁶*, R ⁷and R * ⁸* be hydrogen independently, or C ₁-C ₃₀alkyl or substituted hydrocarbon radical, preferable methyl, ethyl, propyl group or butyl, preferred R ¹*, R ²*, R ³and R * ⁴* be methyl;

R ⁹and R * ¹³* be hydrogen independently separately, or C ₁-C ₃₀alkyl or substituted hydrocarbon radical, preferred C ₂-C ₆alkyl, preferred ethyl;

R ¹⁰*, R ¹¹*, R ¹²* be hydrogen or C independently ₁-C ₃₀alkyl or substituted hydrocarbon radical, preferred hydrogen or methyl;

Each G is hydrogen independently, halogen or C ₁-C ₃₀substituted or unsubstituted alkyl (preferred C ₁-C ₃₀substituted or unsubstituted alkyl or substituted or unsubstituted C ₄-C ₃₀aryl);

Wherein any two adjacent R bases can form the monocycle of maximum 8 non-hydrogen atoms or the polycyclic ring system of maximum 30 non-hydrogen atoms.

Preferably, any two adjacent R bases can form the fused rings with 5-8 non-hydrogen atom.Preferably, non-hydrogen atom is C and/or O.Preferably, adjacent R base forms 5-6 annular atoms, the fused rings of a preferred 5-6 carbon atom.Adjacently refer to that any two R bases are located adjacent to each other, such as R ³and R * ⁴* ring can be formed, and/or R ¹¹and R * ¹²* ring can be formed.

In preferred embodiments, metathesis catalysis immunomodulator compounds comprise following in one or more of: 2-(2,6-diethyl phenyl)-3,5,5,5-tetramethylpyrrolidi-e ketone [2-(isopropoxy)-5-(N, N-dimethylamino-sulfonyl) phenyl] methylene chloride ruthenium; 2-(1，3，5-trimethyl-benzene base)-3,3,5,5-tetramethylpyrrolidi-e ketone [2-(isopropoxy)-5-(N, N-dimethylamino-sulfonyl) phenyl] methylene chloride ruthenium; 2-(2-sec.-propyl)-3,3,5,5-tetramethylpyrrolidi-e ketone [2-(isopropoxy)-5-(N, N-dimethylamino-sulfonyl) phenyl] methylene chloride ruthenium; 2-(2,6-diethyl-4-fluorophenyl)-3,3,5,5-tetramethylpyrrolidi-e ketone [2-(isopropoxy)-5-(N, N-dimethylamino-sulfonyl) phenyl] methylene chloride ruthenium, or its mixture.

About the further information of this olefin metathesis catalyst, refer to the USSN12/939054 submitted on November 3rd, 2010, it requires right of priority and the rights and interests of the USSN61/259514 that on November 9th, 2009 submits to.

The catalyzer of above-mentioned name is usually available from Sigma-AldrichCorp. (St.Louis, MO) or StremChemicals, Inc. (Newburyport, MA).

Cyclic hydrocarbon group monomer

The suitable cyclic hydrocarbon group monomer with at least one internal double bond comprises the C with one or more internal double bond ₃-C ₂₀cyclic hydrocarbon group monomer.This cyclic hydrocarbon group monomer can replace or not replace.Suitable substituting group comprises C ₁-C ₅hydrocarbyl substituent (these substituting groups also can be substituted) (such as, methyl, ethyl, propyl group, butyl, amyl group, and isomer), halogen atom (such as, Br, Cl, I or F), ether substituting group, and similar group.Preferred cyclic hydrocarbon group monomer comprises C ₃-C ₂₀alkyl or substituted hydrocarbon radical, preferred C ₃-C ₁₄alkyl or substituted hydrocarbon radical, preferred C ₃-C ₁₂(substituting group preferably on substituted hydrocarbon radical is C for alkyl or substituted hydrocarbon radical ₁-C ₅alkyl or C ₁-C ₅substituted hydrocarbon radical (such as, methyl, ethyl, propyl group, butyl, amyl group, or its isomer), halogen atom (such as, Br, Cl, I or F), or ether (such as, alkyl oxide or aryl ethers), wherein alkyl is C ₁-C ₂₀alkyl and aryl are C ₆-C ₂₀aryl, preferable methyl ether, ethyl ether, methyl ethyl ether, butyl ether, propyl ether, and similar group).Preferred cyclic hydrocarbon group monomer comprises dicyclo and three ring monomers.Preferred cyclic hydrocarbon group monomer comprises such as cyclopropylene, cyclobutene, cyclopentenes, tetrahydrobenzene, tetrahydrotoluene, suberene, cyclooctadiene, cyclooctene, norbornadiene, norbornylene, cyclobutadiene, cyclohexadiene, cycloheptadiene, cyclooctatetraene, 1,5-cyclooctadiene, 1,5-dimethyl-1,5-cyclooctadiene, Dicyclopentadiene (DCPD), and isomer.Internal double bond refers to that double bond is inner in ring texture, and is not that side hangs on it.Such as, vinyl cyclohexane is not the cyclic hydrocarbon group monomer with at least one internal double bond, and tetrahydrobenzene is the cyclic hydrocarbon group monomer with at least one internal double bond.

The polyolefinic dimer of ethenyl blocking

The polyolefinic dimer of ethenyl blocking useful herein comprises with chemical formula: PO-C=C-PO* represent those, wherein PO and PO* is polyolefine, preferred PO and PO* is independently of one another for having 9-10,000 carbon atom (preferred 20-7500 carbon atom, preferred 30-4000, preferred 40-2000) substituted or unsubstituted alkyl, at least one in preferred PO and PO* has 20-10,000 carbon atom, preferred 30-2000.Preferably, PO and PO* is any combination described herein.For object of the present invention, when using term dimer, it refers to two monomeric units (they can be identical or different), and such as PO and PO* can be identical or different.

In preferred embodiments, the useful dimer represented by formula (X) or its isomer:

PO-C(R ¹¹)(R ¹²)-C(R ¹³)＝C(R ¹⁴)-C(R ¹⁵)(R ¹⁶)-PO*(x),

Wherein R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵and R ¹⁶be substituted or unsubstituted C independently of one another ₁-C ₄alkyl or hydrogen;

PO and PO* is polyolefine independently of one another, and preferably by the polyolefin derivative of ethenyl blocking, preferred PO and PO* is independently of one another for having the substituted or unsubstituted alkyl of 9-4000 carbon atom, and condition is at least one in PO and PO* is C ₂₀or larger, described dimer has:

1) pass through at about 128 to about 132ppm places ¹³interior degree of unsaturation shown in CNMR;

2) ratio " the Z "=0.1-10 of Mn, preferred 0.25-4, preferred 0.5-2, preferred 0.75-1.5, wherein Z is that (this passes through Mn ¹³cNMR measures) divided by Mn (this is by gel permeation chromatography, uses polystyrene standards to measure); With

3) optionally, pass through ¹spectrometric every 1000 carbon of HNMR, (preferably 0.35 (J) is to 0.70 (J) to have 0.30 (J) to 0.75 (J), preferably 0.40 (J) is to 0.60 (J)) interior degree of unsaturation, wherein J is that PO and PO* is by before olefin metathesis catalyst coupling, for the polyolefine of ethenyl blocking, relative to every 1000 carbon, preferably become the quantity of the reactive group of PO and PO*.

For the dimer of formula (X), preferred embodiment has different PO and PO*.In formula (X), PO and PO* can be any PO and PO* described herein.

In another embodiment, dimer has relative to every 1000 carbon, and degree of unsaturation in 0.10-35, this passes through ¹³cNMR measures (being the co-applications USSN13/072383 of " Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock prepared by cross metathesis " as the title submitted on March 25th, 2011), or 0.2-20, preferred 0.3-10.

Produce the polyolefinic dimeric method of ethenyl blocking

By the method comprised the steps, produce the polyolefinic dimer of ethenyl blocking: olefin metathesis catalyst is contacted with the polyolefine of two or more ethenyl blockings, wherein there is the allyl chain ends (relative to whole degree of unsaturation) of at least 30% separately.

Typically in reaction vessel, at 20-200 DEG C of (preferred 50-160 DEG C, preferred 60-140 DEG C) temperature under, with at 0-1000MPa (preferred 0.5-500MPa, preferred 1-250MPa) pressure under, the residence time of combine reactants (comprising the polyolefine of ethenyl blocking, such as PO and PO* is by the polyolefine of its derivative ethenyl blocking) 0.5 second-10 hours (preferably 1 second-5 hours, preferably 1 minute-1 hour).

Typically, relative to the polyolefine of the ethenyl blocking that every Mol introduces, by 0.00001-1.0mol, preferred 0.0001-0.05mol, preferred 0.0005-0.01mol catalyzer is incorporated in reactor.

The method typically is solution method, although it can be body or high-pressure process.Preferred homogeneous method.(homogeneous method is defined as the method that wherein at least 90wt% product is solvable in reaction medium.) especially preferred body homogeneous method.(concentration that substance law is defined as reactant in all raw materials wherein in reactor is more than or equal to 70 volume %.) or there is not solvent or thinner, or do not have solvent or thinner to join in reaction medium, (exception be the carrier being used as in a small amount catalyzer or other additives, or typically find the consumption together with reactant, such as, propane in propylene).

In preferred embodiments, the productivity of the method be the dimer/mmol catalyzer of at least 200g formula (X)/hour, preferably at least 5000g/mmol/h, preferably at least 10,000g/mmol/h, preferably at least 300,000g/mmol/h.

About useful dimer and the more information preparing this dimeric method, refer to the co-applications USSN13/072383 that the title submitted on March 25th, 2011 is " Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock prepared by cross metathesis " herein.

The polyolefine of the alkene of ethenyl blocking

The polyolefine (oligopolymer and polymkeric substance) manufacturing the alkene of the useful ethenyl blocking of dimeric this paper useful herein can comprise the polyolefine of any ethenyl blocking, comprising by one or more of C ₂, C ₃, C ₄to C ₁₂unsaturated monomer prepare those.Suitable monomer includes, but not limited to such as ethene, propylene, butylene class, amylene class, hexene class, heptene class, octene class, nonene class, decene class, and analogue, preferably there is the allyl chain ends of at least 30% separately, relative to whole degree of unsaturation (preferably at least 40%, preferably at least 50%, preferably at least 60%, preferably at least 65%, preferably at least 75%, preferably at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95%).

In preferred embodiments, the polyolefine of ethenyl blocking useful herein comprises at least 10mol% (preferably at least 20mol%, preferably at least 40mol%, preferably at least 60mol%) C ₄or larger alkene (such as, butylene, amylene, octene, nonene, decene, undecylene, dodecylene) and to have: 1) at least 30% allyl chain ends (relative to whole degree of unsaturation), preferably at least 40%, preferably at least 50%, preferably at least 60%, preferably at least 70%, preferably at least 75%, preferably at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95%; With 2) Mn is 200-60,000g/mol, preferred 200-50,000g/mol, preferred 500-40,000g/mol.

The polyolefine of ethenyl blocking used in the present invention comprises containing propylene and is less than 0.5wt% comonomer, the propene polymer of preferred 0wt% comonomer, and wherein this oligopolymer has:

I) at least 93% allyl chain ends (preferably at least 95%, preferably at least 97%, preferably at least 98%);

Ii) number-average molecular weight (Mn) is about 500-about 20,000g/mol, and this passes through ¹hNMR measures (preferred 500-15,000, preferred 700-10,000, preferred 800-8,000g/mol, preferred 900-7000, preferred 1000-6000, preferred 1000-5000);

Iii) the isobutyl-end of the chain is 0.8:1 to 1.3:1.0 with the ratio of allylic vinyl; With

Iv) 1400ppm aluminium (be preferably less than 1200ppm, be preferably less than 1000ppm, be preferably less than 500ppm, be preferably less than 100ppm) is less than.

The polymkeric substance of ethenyl blocking used in the present invention also comprises and passing through ¹the Mn that HNMR measures is 300-30, 000g/mol (preferred 400-20, 000, preferred 500-15, 000, preferred 600-12, 000, preferred 800-10, 000, preferred 900-8000, preferred 900-7000g/mol) propylene copolymer, described propylene copolymer comprises 10-90mol% propylene (preferred 15-85mol%, preferred 20-80mol%, preferred 30-75mol%, preferred 50-90mol%) and 10-90mol% (preferred 85-15mol%, preferred 20-80mol%, preferred 25-70mol%, preferred 10-50mol%) one or more of alpha-olefin comonomer (optimal ethylene, butylene, hexene, or octene, optimal ethylene), wherein this oligopolymer has at least X% allyl chain ends (relative to whole degree of unsaturation), wherein: 1) X=(-0.94 (ethene that mol% mixes)+100{ or 1.20 (-0.94 (ethene that mol% mixes)+100), or 1.50 (-0.94 (ethene that mol% mixes)+100) }), when 10-60mol% ethene is present in this altogether-oligopolymer, with 2) X=45 (or 50, or 60), when be greater than 60 and be less than 70mol% ethene be present in this multipolymer time, with 3) X=(1.83* (ethene that mol% mixes)-83, or 1.20 [1.83* (ethene that mol% mixes)-83], or 1.50 [1.83* (ethene that mol% mixes)-83] }), when 70-90mol% ethene is present in this multipolymer.Or X is more than or equal to 80%, preferably greater than or equal to 85%, preferably greater than or equal to 90%, preferably greater than or equal to 95%.In an alternative embodiment, polymkeric substance has the isobutyl-end of the chain (based on isobutyl-and the saturated end of the chain sum of n-propyl) of at least 80%, the preferably at least 85% isobutyl-end of the chain, the preferably at least 90% isobutyl-end of the chain.Or the isobutyl-end of the chain that this polymkeric substance has is 0.8:1 to 1.35:1.0 with the ratio of allylic vinyl, preferred 0.9:1 to 1.20:1.0, preferred 0.9:1.0 to 1.1:1.0.

The olefin polymer of ethenyl blocking used in the present invention also comprises propene polymer, described propene polymer comprises and is greater than 90mol% propylene (preferred 95-99mol%, preferred 98-9mol%) and be less than 10mol% ethene (preferred 1-4mol%, preferred 1-2mol%), wherein this polymkeric substance has:

Ii) number-average molecular weight (Mn) is about 400-about 30,000g/mol, and this passes through ¹hNMR measures (preferred 500-20,000, preferred 600-15,000, preferred 700-10,000g/mol, preferred 800-9000, preferred 900-8000, preferred 1000-6000);

Iii) the isobutyl-end of the chain is 0.8:1 to 1.35:1.0 with the ratio of allylic vinyl; With

Olefin polymer and the polymkeric substance of ethenyl blocking used in the present invention also comprise propene polymer, described propene polymer comprises at least 50 (preferred 60-90, preferred 70-90) mol% propylene and 10-50 (preferred 10-40, preferred 10-30) mol% ethene, wherein this polymkeric substance has:

I) at least 90% allyl chain ends (preferably at least 91%, preferably at least 93%, preferably at least 95%, preferably at least 98%);

Ii) Mn is about 150-about 20,000g/mol, and this passes through ¹hNMR measures (preferred 200-15,000, preferred 250-15,000, preferred 300-10,000, preferred 400-9500, preferred 500-9000, preferred 750-9000); With

Iii) the isobutyl-end of the chain is 0.8:1 to 1.3:1.0 with the ratio of allylic vinyl, wherein

There is the monomer being more than or equal to 4 carbon atoms exist with 0-3mol% (be preferably less than 1mol%, be preferably less than 0.5mol%, preferred 0mol%).

The olefin polymer of ethenyl blocking used in the present invention also comprises propene polymer, and described propene polymer comprises:

At least 50 (preferably at least 60, preferred 70-99.5, preferred 80-99, preferred 90-98.5) mol% propylene, 0.1-45 (or at least 35, preferred 0.5-30, preferred 1-20, preferred 1.5-10) mol% ethene, and the C of 0.1-5 (preferred 0.5-3, preferred 0.5-1) mol% ₄-C ₁₂alkene (such as, butylene, hexene, or octene, preferred butylene), wherein this polymkeric substance has:

Ii) number-average molecular weight (Mn) is about 150-about 15,000g/mol, and this passes through ¹hNMR measures (preferred 200-12,000, preferred 250-10,000, preferred 300-10,000g/mol, preferred 400-9500, preferred 500-9000, preferred 750-9000); With

Iii) the isobutyl-end of the chain is 0.8:1 to 1.35:1.0 with the ratio of allylic vinyl.

At least 50 (preferably at least 60, preferred 70-99.5, preferred 80-99, preferred 90-98.5) mol% propylene, 0.1-45 (or at least 35, preferred 0.5-30, preferred 1-20, preferred 1.5-10) mol% ethene, and 0.1-5 (preferred 0.5-3, preferred 0.5-1) mol% diolefine (such as, C ₄-C ₁₂α-ω (omega) alkene (such as, divinyl, hexadiene, octadiene), norbornadiene, ethylidene norbornene, vinyl norbornene, norbornadiene, and Dicyclopentadiene (DCPD)), wherein this polymkeric substance has:

Ii) number-average molecular weight (Mn) is about 150-about 20,000g/mol, and this passes through ¹hNMR measures (preferred 200-15,000, preferred 250-12,000, preferred 300-10,000g/mol, preferred 400-9500, preferred 500-9000, preferred 750-9000); With

Iii) the isobutyl-end of the chain is 0.7:1 to 1.35:1.0 with the ratio of allylic vinyl.

In another embodiment, the polyolefine of useful herein ethenyl blocking can be that (this passes through Mn ¹hNMR measures) for being more than or equal to 200g/mol (preferred 300-60,000g/mol, 400-50,000g/mol, preferred 500-35,000g/mol, preferred 300-15,000g/mol, preferred 400-12,000g/mol, or preferably 750-10,000g/mol) the polymkeric substance of one or more of ethenyl blockings, and this polymkeric substance comprises: (i) about 20-is about at least one C of 99.9mol% (preferably about 25-is about 90mol%, and about 30-is about 85mol%, and about 35-is about 80mol%, and about 40-is about 75mol%, or about 50-is about 95mol%) ₅-C ₄₀alkene (preferred C ₅-C ₃₀alpha-olefin, more preferably C ₅-C ₂₀alpha-olefin, preferred C ₅-C ₁₂alpha-olefin, preferred amylene, hexene, heptene, octene, nonene, decene, undecylene, dodecylene, norbornylene, norbornadiene, Dicyclopentadiene (DCPD), cyclopentenes, suberene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, its substitutive derivative, and isomer, preferred hexane, heptene, octene, nonene, decene, dodecylene, cyclooctene, 1, 5-cyclooctadiene, 1-hydroxyl-4-cyclooctene, 1-acetoxyl group-4-cyclooctene, 5-methyl cyclopentene, cyclopentenes, Dicyclopentadiene (DCPD), norbornylene, norbornadiene and Dicyclopentadiene (DCPD)), (ii) about 0.1-80mol% propylene (preferably about 5%-70mol%, about 10-65mol%, about 15-55mol%, about 25-50mol%, or about 30-80mol%), wherein the polyolefine of ethenyl blocking has the allyl chain ends (preferably at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%) of at least 40%, optionally, the isobutyl-end of the chain and the ratio of allyl chain ends are less than 0.70:1 (be preferably less than 0.65:1, be less than 0.60:1, be less than 0.50:1, or be less than 0.25:1), further, optionally, (this passes through for allyl chain ends and the vinylidene base end of the chain ¹hNMR measure) ratio be greater than 2:1 (be preferably greater than 2.5:1, be greater than 3:1, be greater than 5:1, or be greater than 10:1), further, optionally, allyl chain ends and the ratio of the vinylidene base end of the chain are greater than 10:1 (be preferably greater than 15:1, or be greater than 20:1), even further optionally, preferably there is no the isobutyl-end of the chain (being preferably less than the 0.1wt% isobutyl-end of the chain).About the polyolefinic further information of this ethenyl blocking, refer to the co-applications USSN13/072249 that the title submitted on March 25th, 2011 is " olefin copolymer of ethenyl blocking and production method thereof ".

In another embodiment, the polyolefine of useful herein ethenyl blocking can be that (this passes through Mn ¹hNMR measures) for being more than or equal to 200g/mol (preferred 300-60,000g/mol, 400-50,000g/mol, preferred 500-35,000g/mol, preferred 300-15,000g/mol, preferred 400-12,000g/mol, or preferred 750-10, the polyolefine of one or more of ethenyl blockings 000g/mol), and it comprises: (i) about 80-99.9mol% (preferred 85-99.9mol%, more preferably 90-99.9mol%) at least one C ₄alkene (preferred 1-ground relation); (ii) about 0.1-20mol% propylene, preferred 0.1-15mol%, more preferably 0.1-10mol%; Wherein the polyolefine of ethenyl blocking has at least 40% allyl chain ends, and preferably at least 50%, at least 60%, at least 70%, at least 80%; Optionally the isobutyl-end of the chain is less than 0.70:1 with the ratio of allyl chain ends, is less than 0.65:1, is less than 0.60:1, be less than 0.50:1, or be less than 0.25:1; Further optionally, allyl chain ends is greater than 2:1 with the ratio of the vinylidene base end of the chain, is greater than 2.5:1, is greater than 3:1, be greater than 5:1, or be greater than 10:1; Further optionally, allyl chain ends and the ratio of the vinylidene end of the chain are greater than 10:1 (be preferably greater than 15:1, or be greater than 20:1); Even further optionally, preferably there is no the isobutyl-end of the chain (being preferably less than the 0.1wt% isobutyl-end of the chain).About the polyolefinic further information of this ethenyl blocking, refer to the co-applications USSN13/072249 that the title submitted on March 25th, 2011 is " olefin copolymer of ethenyl blocking and production method thereof ".

In the special embodiment of this paper, the present invention relates to a kind of composition, it comprises Mn, and (this passes through ¹hNMR measures) be at least 200g/mol (preferred 200-100,000g/mol, preferred 200-75,000g/mol, preferred 200-60,000g/mol, preferred 300-60,000g/mol, or preferably 750-30,000g/mol) the polyolefine of ethenyl blocking, and it comprise one or more of (preferably two or more, three kinds or more kind, plants by four kinds or more, and analogue) C ₄-C ₄₀(preferred C ₄-C ₃₀, C ₄-C ₂₀, or C ₄-C ₁₂, preferred butylene, amylene, hexene, heptene, octene, nonene, decene, undecylene, dodecylene, norbornylene, norbornadiene, Dicyclopentadiene (DCPD), cyclopentenes, suberene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, its substitutive derivative, and isomer) the derivative unit of higher alkene, wherein the olefin polymer of ethenyl blocking goes up the unit (being preferably less than 0.1wt% propylene) not comprising propylene derived substantially; Wherein higher olefin polymer (at least 10%, at least 15%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95%) allyl chain ends that has at least 5%; Optionally, allyl chain ends and the ratio of the vinylidene base end of the chain are greater than 2:1 (be preferably greater than 2.5:1, be greater than 3:1, be greater than 5:1, or be greater than 10:1); Further optionally, allyl chain ends is greater than 10:1 with the ratio of the vinylidene end of the chain and (is preferably greater than 15:1.Or be greater than 20:1); Even further optionally, preferably not there is the isobutyl-end of the chain (being preferably less than the 0.1wt% isobutyl-end of the chain) substantially.In some embodiments, the polymkeric substance of the ethenyl blocking of these higher alkenes can comprise the unit of ethylene derivative, preferably at least 5mol% ethene (preferably at least 15mol% ethene, preferred at least 25mol% ethene, preferably at least 35mol% ethene, preferably at least 45mol% ethene, preferably at least 60mol% ethene, preferred at least 75mol% ethene, or preferred at least 90mol% ethene).About the further information of the alkaline source of this ethenyl blocking, refer to the co-applications USSN13/072288 that the title submitted on March 25th, 2011 is " olefin copolymer of ethenyl blocking and production method thereof ".

In another embodiment, the polyolefine of useful herein ethenyl blocking comprises one or more of alhpa olefin (optimal ethylene and/or propylene and optionally C ₄-C ₁₀alhpa olefin) branched polyolefins, its Mn is 7500-60,000g/mol (with optionally Tm be greater than 60 DEG C (being preferably greater than 100 DEG C) and or optionally Δ Hf be greater than 7J/g (being preferably greater than 50J/g)), described branched polyolefins has (i) and is more than or equal to 50mol% allyl chain ends, relative to whole undersaturated end of the chain (preferably greater than or equal to 60%, preferably greater than or equal to 70%, preferably greater than or equal to 80%, preferably greater than or equal to 90%, preferably greater than or equal to 95%); (ii) g'(vis) be less than or equal to for 0.90 (be preferably less than or equal to 0.85, be preferably less than or equal to 0.80); (iii) optionally, allyl chain ends is greater than 5:1 (being preferably greater than 10:1) with the ratio of interior vinylidene base; (iv) optionally, allyl chain ends is greater than 10:1 (being preferably greater than 15:1) with the ratio of the vinylidene base end of the chain.

In another embodiment, the polyolefine of useful herein ethenyl blocking comprises one or more of alhpa olefin (optimal ethylene and/or propylene and optionally C ₄-C ₁₀alhpa olefin) branched polyolefins, its Mn is for being more than or equal to 60,000g/mol (with optionally Tm be greater than 60 DEG C (being preferably greater than 100 DEG C) and or optionally Δ Hf be greater than 7J/g (being preferably greater than 50J/g)), described branched polyolefins has (i) and is more than or equal to 50mol% allyl chain ends, relative to whole undersaturated end of the chain (preferably greater than or equal to 60%, preferably greater than or equal to 70%, preferably greater than or equal to 80%, preferably greater than or equal to 90%, preferably greater than or equal to 95%); (ii) g'(vis) be less than or equal to for 0.90 (be preferably less than or equal to 0.85, be preferably less than or equal to 0.80); (iii) when complete hydrogenation, bromine number decline at least 50% (preferably at least 75%); (iv) optionally, allyl chain ends is greater than 5:1 (being preferably greater than 10:1) with the ratio of interior vinylidene base; (v) optionally, allyl chain ends is greater than 10:1 (being preferably greater than 15:1) with the ratio of the vinylidene base end of the chain.

In another embodiment, the polyolefine of useful herein ethenyl blocking comprises one or more of alhpa olefin (optimal ethylene and/or propylene and optionally C ₄-C ₁₀alhpa olefin) branched polyolefins, its Mn is for being less than 7500g/mol, preferred 100-7500g/mol (with optionally Tm be greater than 60 DEG C (being preferably greater than 100 DEG C) and or optionally Δ Hf be greater than 7J/g (being preferably greater than 50J/g)), described branched polyolefins has (i) and is more than or equal to 50mol% allyl chain ends, relative to whole undersaturated end of the chain (preferably greater than or equal to 60%, preferably greater than or equal to 70%, preferably greater than or equal to 80%, preferably greater than or equal to 90%, preferably greater than or equal to 95%); (ii) saturated end of the chain % and the ratio of allyl chain ends % are 1.2-2.0 (preferred saturated end of the chain % (the preferred isobutyl-end of the chain) is 1.6-1.8 with the ratio of allyl chain ends %), wherein as described in the paragraph [0095] of WO2009/155471 and [0096], use ¹³cNMR, measures saturated end of the chain %, and difference is this spectral reference solvent, tetrachloroethane-d ₂chemical shift; And/or Mn (GPC)/Mn ( ¹hNMR) ratio was less than or equal to for 0.95 (be preferably less than or equal to 0.90, be preferably less than or equal to 0.85, be preferably less than or equal to 0.80); (iii) optionally, when complete hydrogenation, bromine number decline at least 50% (preferably at least 75%); (iv) optionally, allyl chain ends is greater than 5:1 (being preferably greater than 10:1) with the ratio of interior vinylidene base; (v) optionally, allyl chain ends is greater than 2:1 (being preferably greater than 10:1) with the ratio of the vinylidene base end of the chain, Mn (GPC)/Mn in the polyolefine of the ethenyl blocking of preferred branched ( ¹hNMR) ratio was less than or equal to for 0.95 (be preferably less than or equal to 0.90, be preferably less than or equal to 0.85, be preferably less than or equal to 0.80).

Can be used for the C in branched chain polymer described above ₄-C ₁₀'alpha '-olefin monomers comprises butylene, amylene, hexene, heptene, octene, nonene, decene, cyclopentenes, suberene, cyclooctene, and isomer.

About the more information of useful branched chain polymer and production method thereof, refer to the co-applications USSN61/467681 that the title submitted on March 25th, 2011 is " polymkeric substance of branched ethylene base end-blocking and production method thereof ".

The polyolefine of the ethenyl blocking be particularly useful can be isotaxy, height isotaxy, syndiotaxy, or highly syndyotactic propene polymer, especially isotactic polyprophlene." isotaxy " used herein is defined as the isotaxy five unit group with at least 10%, preferably basis ¹³c-NMR analyzes, and has at least 40% by the isotaxy five unit group of the methyl of propylene derived." height isotaxy " used herein is defined as basis ¹³c-NMR analyzes, and has the isotaxy five unit group of at least 60%.In required embodiment, PO, and/or PO* and/or produce the degree of isotacticity that the polyolefine of ethenyl blocking that PO and PO* use has at least 85%." syndiotaxy " used herein is defined as basis ¹³c-NMR analyzes, and has at least 10% syndyotactic five unit groups, and preferably at least 40%." height syndiotaxy " used herein is defined as basis ¹³c-NMR analyzes, and has the syndiotaxy five unit group of at least 60%.In another embodiment, PO, and/or PO* and/or produce the degree of syndiotacticity that the polyolefine of ethenyl blocking that PO and PO* use has at least 85%.

The polyolefine of any ethenyl blocking described herein preferably has and is less than 1400ppm aluminium, is preferably less than 1000ppm aluminium, is preferably less than 500ppm aluminium, be preferably less than 100ppm aluminium, be preferably less than 50ppm aluminium, be preferably less than 20ppm aluminium, be preferably less than 5ppm aluminium.

Cross-metathesis product disclosed herein seldom or not has reactive terminal group, and this passes through ¹³in CNMR spectrum, in about 128-132ppm place, unsaturated peak is more than or equal to 2.0 with the intensity ratio in about 114 and 137ppm place reactive end base peak proved.

In preferred embodiments, the polyolefine of any ethenyl blocking described herein comprises and is less than 3wt% and is selected from oxyhydroxide (hydroxide), aryl and substituted aryl, halogen, alkoxyl group, carboxylicesters, ester, acrylate, oxygen, nitrogen, and the functional group in carboxyl, be preferably less than 2wt%, be more preferably less than 1wt%, be more preferably less than 0.5wt%, be more preferably less than 0.1wt%, more preferably 0wt%, based on the weight of oligopolymer.

The polyolefine of preferred ethenyl blocking described herein passes through ¹the M that HNMR measures _nfor 150-25,000g/mol, 200-20,000g/mol, preferred 250-15,000g/mol, preferred 300-15,000g/mol, preferred 400-12,000g/mol, preferred 750-10,000g/mol.Molecular weight ranges required further can be any combination of above-described any upper limit molecular weight and any lower limit molecular weight.According to the method described in following examples part, measure M _n.

The polyolefinic second-order transition temperature (Tg) of any ethenyl blocking described herein is less than or equal to 0 DEG C (this is by determine with dsc method of the following stated), preferably be less than or equal to-10 DEG C, be more preferably less than or equal-20 DEG C, be more preferably less than or equal-30 DEG C, be more preferably less than or equal-50 DEG C.

The polyolefine of any ethenyl blocking described herein is preferably containing the C being less than 80wt% ₄alkene (such as, n-butene, 2-butylene, iso-butylene and divinyl), based on the weight of oligopolymer, preferably be less than 10wt%, preferred 5wt%, is preferably less than 4wt%, is preferably less than 3wt%, preferably be less than 2wt%, be preferably less than 1wt%, be preferably less than 0.5wt%, be preferably less than the C of 0.25wt% ₄alkene, based on polyolefinic weight.

Or the polyolefine of any ethenyl blocking described herein is preferably containing the C being less than 20wt% ₄or more senior alkene (such as, C ₄-C ₃₀alkene, typically such as C ₄-C ₁₂alkene, typically such as C ₄, C ₆, C ₈, C ₁₂alkene etc.), based on polyolefinic weight, be preferably less than 10wt%, preferred 5wt%, is preferably less than 4wt%, is preferably less than 3wt%, is preferably less than 2wt%, is preferably less than 1wt%, is preferably less than 0.5wt%, is preferably less than the C of 0.25wt% ₄alkene, based on polyolefinic weight, this passes through ¹³cNMR measures.

In another embodiment, the polyolefine of any ethenyl blocking described herein comprises at least 50wt% (preferably at least 75wt%, preferred at least 90wt%, weight based on oligomeric composition) there are at least 36 carbon atoms (preferably at least 51 carbon atoms, preferably at least 102 carbon atoms) alkene, this supposes every bar chain 1 degree of unsaturation, passes through ¹hNMR measures.

In another embodiment, the polyolefine of any ethenyl blocking described herein contains and is less than 20wt% dimer and tripolymer (is preferably less than 10wt%, is preferably less than 5wt%, be preferably less than 2wt%, weight based on oligomeric composition), this passes through gas chromatography determination.By vapor-phase chromatography (having the Agilent6890N of automatic injector), use helium as vector gas, assay products under 38cm/s.Use is filled with the pillar (J & WScientificDB-1,60m × 0.25mmI.D. × 1.0 μm thickness) of the long 60m of flame ionization detector (FID), the injector temperature of 250 DEG C, and the detector temperature of 250 DEG C.In baking oven, at 70 DEG C, by Sample Injection in pillar, be then heated in 22 minutes 275 DEG C (temperature rise rate 10 DEG C/min to 100 DEG C, keeps by 30 DEG C/min to 275 DEG C).Use interior mark, usual monomer, the derive dimer or trimer product amount that obtain.According to the data that photometer records, calculate the output of dimer and trimer product.Relative to interior mark, by the area under the Relative Peak on GC curve, calculate the amount of dimer or trimer product.

In another embodiment, the polyolefine of any ethenyl blocking described herein contains and is less than 25ppm hafnium, is preferably less than 10ppm hafnium, is preferably less than 5ppm hafnium, based on the output of produced product and the quality of the catalyzer used.

In another embodiment, the polyolefinic fusing point (DSC first melting) of any ethenyl blocking described herein can be 60-130 DEG C, or 50-100 DEG C.In another embodiment, after storing at least 48 hours under envrionment temperature (23 DEG C), polyolefine described herein does not have by the detectable fusing point of DSC.

Use dsc (DSC), use commercially available equipment, such as TAInstruments2920DSC, measure melt temperature (Tm) and second-order transition temperature (Tg).Typically, the 6-10mg sample at room temperature storing at least 48 hours is sealed in aluminium dish, and at room temperature, load is in this instrument.At 25 DEG C, balance this sample, be then cooled to-80 DEG C with the speed of cooling of 10 DEG C/min.At-80 DEG C, keep sample 5 minutes, then under the rate of heating of 10 DEG C/min, be heated to 25 DEG C.According to this heating cycle, measure second-order transition temperature.Or, balance sample at 25 DEG C.Then under the rate of heating of 10 DEG C/min, 150 DEG C are heated to.Start and peak temperature for transformation, analyze heat absorption melting transition (if the words existed).The melt temperature reported is the peak melt temperature from first time heating, except as otherwise noted.For the sample demonstrating multiple peak, definition fusing point (or melt temperature) is the peak melt temperature (namely replying relevant with the maximum heat absorption calorimetric in this temperature range) from DSC melting curve.

In another embodiment, the polyolefine of any ethenyl blocking described herein is liquid at 25 DEG C.

Bromine number is measured by ASTMD1159.Be used in J.W.Olesik, in EncyclopediaofMaterialsCharacterization " InductivelyCoupledPlasma-OpticalEmissionSpectroscopy; " C.R.Brundle, C.A.Evans, Jr. and S.Wilson edit, Butterworth-Heinemann, Boston, Mass., 1992, the ICPES (inductively coupled plasma emission spectrography) described in 633-644 page, is determined at the content of a kind of element in material.

In another embodiment, the viscosity of polymkeric substance at 60 DEG C of ethenyl blocking described herein is greater than 1000cP, is greater than 12,000cP, or is greater than 100,000cP.In other embodiments, the viscosity of the polymkeric substance of ethenyl blocking is less than 200,000cP, is less than 150,000cP, or is less than 100,000cP.Use Brookfield Digital Viscometer, measure viscosity.

In another embodiment, to describe herein or the polyolefine of useful any ethenyl blocking has the 3-alkyl vinyl end group represented with following formula (wherein alkyl is C ₁-C ₃₈alkyl), also referred to as " the 3-alkyl end of the chain " or " 3-alkyl vinyl end group ":

Wherein " " represents polyolefin chain, and R ^bc ₁-C ₃₈alkyl, preferred C ₁-C ₂₀alkyl, such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, and similar group.Use following to list ¹³cNMR, measures the looking somebody up and down of 3-alkyl chain.

In preferred embodiments, the polyolefine of description or useful any ethenyl blocking has the 3-alkyl end of the chain (the preferably 3-alkyl end of the chain of at least 10% of at least 5% herein, the 3-alkyl end of the chain of at least 20%, the 3-alkyl end of the chain of at least 30%, the 3-alkyl end of the chain of at least 40%, the 3-alkyl end of the chain of at least 50%, the 3-alkyl end of the chain of at least 60%, the 3-alkyl end of the chain of at least 70%, the 3-alkyl end of the chain of at least 80%, the 3-alkyl end of the chain of at least 90%, the 3-alkyl end of the chain of at least 95%), relative to whole degree of unsaturation.

In preferred embodiments, the polyolefine of description or useful any ethenyl blocking has the 3-alkyl+allyl chain ends (such as all 3-alkyl end of the chains add all allyl chain ends) of at least 5% herein, the preferably 3-alkyl+allyl chain ends of at least 10%, 3-alkyl+the allyl chain ends of at least 20%, 3-alkyl+the allyl chain ends of at least 30%, 3-alkyl+the allyl chain ends of at least 40%, 3-alkyl+the allyl chain ends of at least 50%, 3-alkyl+the allyl chain ends of at least 60%, 3-alkyl+the allyl chain ends of at least 70%, 3-alkyl+the allyl chain ends of at least 80%, 3-alkyl+the allyl chain ends of at least 90%, 3-alkyl+the allyl chain ends of at least 95%, relative to whole degree of unsaturation.

In another embodiment, the polyolefinic Mw (measuring as mentioned above) of ethenyl blocking described herein is 1000-about 30,000g/mol, or 2000-25,000g/mol, or 3000-20,000g/mol, and/or Mz is about 1700-about 150,000g/mol, or 800-100,000g/mol.

Three on-line checkingi devices are furnished with: the Temperature Size Exclusion chromatographic instrument (available from WatersCorporation or PolymerLaboratories) of differential refractive index detector (DRI), scattering of light (LS) detector and viscometer by using, measure Mw, Mn, Mz, amount of carbon atom, and g'vis.Experimental detail, the correction comprising detector is disclosed in T.Sun, P.Brant, R.R.Chance, and W.W.Graessley, Macromolecules, the 34th volume, the 19th phase, in 6812-6820 page (2001) and the reference in it.Use three PolymerLaboratoriesPLgel10mmMixed-BLS pillars.Nominal flow rate is 0.5cm ³/ min, and the volume injected of nominal is 300 microlitres.Various transfer line, pillar and differential refractometer (DRI detector) are contained in the baking oven that maintains at 145 DEG C.By dissolving the butylated hydroxytoluene of 6g as oxidation inhibitor in 4 liters of Aldrich SILVER REAGENT 1,2,4-trichlorobenzene (TCB), preparation experiment solvent.Then TCB mixture is filtered through the glass prefilter of 0.7 micron, and subsequently by the Teflon strainer of 0.1 micron.Then, before entering in size exclusion chromatography instrument, make TCB degassed with online degasser.By the polymkeric substance of drying is placed in Glass Containers, adds the TCB of aequum, then at 160 DEG C, heat this mixture with continuous stirring about 2 hours, prepare polymers soln.All amount gravity methods are measured.At room temperature, the TCB density (mass/volume unit) that expression polymer concentration uses is 1.463g/ml, and is 1.324g/ml at 145 DEG C.Injection concentration is 0.75-2.0mg/ml, and low concentration is used for the sample of higher molecular weight.Before each sample runs, purification DRI detector and syringe.Then the flow velocity in raising device to 0.5ml/min, and before injection first sample, allows DRI to stablize 8-9 hour.Before operation sample, open LS laser apparatus 1-1.5 hour.According to the DRI signal of baseline-deduct, I _dRI, use following equation, calculate the concentration c at every bit place in color atlas:

c＝K _DRII _DRI/(dn/dc)

Wherein K _dRIbe the constant measured by correcting DRI, and (dn/dc) is the refractive index incremental change (increment) of this system.For TCB, at 145 DEG C, refractive index, n=1.500, and λ=690nm.For the object of the present invention and claims, (dn/dc)=0.104 of propene polymer, butene polymers is 0.098, and in other cases, is 0.1.In the middle of this explanation of SEC method, the unit of parameter makes concentration with g/cm ³express, molecular weight is expressed with g/mol, and intrinsic viscosity is expressed with dL/g.

LS detector is the minimum-DAWN of WyattTechnology high temperature.By using the Zimm model being used for static light scattering, analyzing LS and exporting, being determined at the molecular weight M (M.B.Huglin, LIGHTSCATTERINGFROMPOLYMERSOLUTIONS, AcademicPress, 1971) at every bit place in color atlas:

\frac{K_{o} c}{ΔR (θ)} = \frac{1}{MP (θ)} + 2 A_{2} c

Herein, Δ R (θ) is the excessive Rayleigh scattering strength measured under scatteringangleθ, and c analyzes the polymer concentration measured, A according to DRI ₂second virial coefficient, for the object of the invention, the A of propene polymer ₂=0.0006, butene polymers is 0.0015, and is 0.001 in other situations, (dn/dc)=0.104 of propene polymer, butene polymers is 0.098, and is 0.1 in other situations, P (θ) is for the form factor monodispersed random coil, and K ₀the best constant of system:

K_{o} = \frac{4 π^{2} n^{2} {(dn / dc)}^{2}}{λ^{4} N_{A}}

Wherein N _abe Avogadro value, and (dn/dc) is the refractive index increment value of system.For TCB at 145 DEG C and λ=690nm, refractive index n=1.500.

Use high temperature ViscotekCoporation viscometer, it has four capillaries arranged in the Wheatstone bridged linkage with pressure transmitter, measures specific viscosity.Sensor measurement across the total pressure drop of detector, the pressure different with another sensor measurement between bridge both sides.According to their output, calculate the proportion η flowing through the solution of viscometer _s.According to following equation, calculate the intrinsic viscosity at every bit place in color atlas:

η _S=c[η]+0.3(c[η]) ²

Wherein c is concentration and exports according to DRI to measure.

As described below, utilize the output of SEC-DRI-LS-VIS method, calculate branch index (g'vis).By the average intrinsic viscosity [η] of following formula calculation sample _avg:

{[η]}_{avg} = \frac{Σ c_{i} {[η]}_{i}}{Σ c_{i}}

Wherein summation is on the chromatogram thin slice i between limit of integration.

Branch index g ' vis is defined as:

g^{'} vis = \frac{{[η]}_{avg}}{k M_{v}^{α}}

Wherein for the object of the present invention and claims, α=0.695 of linear tetrafluoroethylene polymer, and k=0.000579, α=0.705 of linear propylene polymer, and k=0.000262, and α=0.695 of linear butylene polymkeric substance, and k=0.000181.Mv is the viscosity-average molecular weight that the molecular weight analyzing mensuration based on LS obtains.See Macromolecules, 2001,34,6812-6820 page and Macromolecules, 2005,38,7181-7183 page is about the linear criterion thing selecting to have similar molecular weight and co-monomer content and measure the guide of k-factor and alpha index.

According to aforesaid method, determining molecular weight distribution (Mw/Mn-all passes through GPC-DRI).In some embodiments, the polyolefinic Mw/Mn (passing through GPC-DRI) of ethenyl blocking of the present invention is 1.5-20, or 1.7-10.

In another embodiment, the material containing any vinyl can be adopted, the material of preferred employing ethenyl blocking is (comprising the polymkeric substance of ethenyl blocking, polyolefine (Alathon of such as ethenyl blocking and the multipolymer of ethenyl blocking, with alfon and the multipolymer of ethenyl blocking)), put into practice the present invention.These materials many are known in the art and can use method described herein, such as make olefin metathesis catalyst (as described herein), containing the cyclic hydrocarbon group monomer of at least one internal double bond, and the one or more of material containing ethenyl blocking, thus reaction.The polymkeric substance of ethenyl blocking comprises homopolymer containing heteroatomic monomer and multipolymer, and the polymkeric substance of only olefinic monomer.(polymkeric substance of term ethenyl blocking comprises the oligopolymer of ethenyl blocking.) polyolefine of preferred ethenyl blocking comprises the isotactic polyprophlene of ethenyl blocking (preferred fusing point is more than or equal to 100 DEG C, preferably greater than or equal to 155 DEG C), polyethylene (preferred fusing point is more than or equal to 100 DEG C, preferably greater than or equal to 155 DEG C).

Manufacture the method for the oligopolymer of ethenyl blocking

Typically in homogeneous method, in the substance law described in preferred WO2009/155471 (at this by reference to being introduced into), prepare the polyolefine of above-described ethenyl blocking.In preferred embodiments, by making catalyst system (it comprises metallocene compound, and one or more of activator) and olefine reaction, oligomerisation of propene and optional comonomer (such as ethene).Also other additives can be used, such as scavenging agent and/or hydrogen.The suspension of any routine, homogeneous phase body, solution, slurry or High pressure oligomerisation method can be used.These methods can be run according to interval, semi-batch or continuous mode.These methods and pattern are well-known in the art.Preferred homogeneous polymerization process.(product that homogeneous polymerization process is defined as wherein at least 90wt% dissolves in the method in reaction medium.) especially preferred body homogeneous method.(substance law is defined as monomer concentration in all raw materials wherein in arrival reactor and is more than or equal to 70 volume %.) or, there is not solvent or thinner or do not add in reaction medium solvent or thinner (exception be the carrier being used as catalyzer or other additives in a small amount, or typically find the consumption together with reactant, such as, propane in propylene).

Can be used for polymerization described herein to produce the polyolefinic monomer of ethenyl blocking and comprise one or more of (preferably two or more, three kinds or more kind, plants by four kinds or more, and analogue) C ₂-C ₄₀(preferred C ₃-C ₃₀, C ₄-C ₂₀, or C ₅-C ₁₂, optimal ethylene, propylene, butylene, amylene, hexene, heptene, octene, nonene, decene, undecylene, dodecylene, norbornylene, norbornadiene, Dicyclopentadiene (DCPD), cyclopentenes, suberene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, its substitutive derivative and isomer thereof).

In some embodiments, when butylene is comonomer, butylene source can be the mixed butene logistics containing various butylene isomer.Expection 1-butylene monomer is preferably consumed by polymerization technique.This mixed butene logistics is used to provide economic advantages, such as, because these mixture flow are usually the waste stream from reforming process, C ₄residual solution logistics, with therefore compared with pure 1-butylene, can be significantly so not expensive.

Suitable diluent/solvent for being polymerized comprises the inert liq of non-coordination.Example comprises straight chain and branched-chain hydrocarbon, such as Trimethylmethane, butane, pentane, iso-pentane, hexane, isohexane, heptane, octane, dodecane, and composition thereof; Ring-type and clicyclic hydrocarbon, such as hexanaphthene, suberane, methylcyclohexane, methylcycloheptane, and composition thereof, such as commercial findable those (Isopars); Perhalogenation hydrocarbon, such as perfluorination C _4-10alkane, chlorobenzene, and the aromatic substance of aromatics and alkyl replacement, such as benzene, toluene, 1，3，5-trimethyl-benzene and dimethylbenzene.Suitable solvent also comprises the liquid olefin can serving as monomer or comonomer, comprising ethene, and propylene, 1-butylene, 1-hexene, 1-amylene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 1-octene and 1-decene.Aforesaid mixture is also suitable.In preferred embodiments, preferred aliphatic series hydrocarbon solvent, such as Trimethylmethane, butane, pentane, iso-pentane, hexane, isohexane, heptane, octane, dodecane, and composition thereof; Ring-type and clicyclic hydrocarbon, such as hexanaphthene, suberane, methylcyclohexane, methylcycloheptane, and composition thereof.In another embodiment, solvent is not aromatic hydrocarbons, and the amount of preferred aromatic hydrocarbons in solvent is less than 1wt%, preferred 0.5wt%, preferred 0wt%, based on the weight of solvent.

In preferred embodiments, do not have in the method or seldom use scavenging agent to produce the polyolefine of ethenyl blocking.Preferably, the amount of scavenging agent is 0mol%, or the amount of scavenging agent is that the mol ratio of scavenging agent metal and transition metal is less than 100:1, is preferably less than 50:1, is preferably less than 15:1, be preferably less than 10:1.

In preferred embodiments, in polymerization reactor, hydrogen is with 0.001-50Psig (0.007-345kPa), preferred 0.01-25psig (0.07-172.4kPa), more preferably the dividing potential drop of 0.1-10psig (0.7-68.95kPa) exists.Find, in system of the present invention, can hydrogen be used, the activity of increase is provided, and significantly do not damage the ability of Catalyst Production allyl chain ends.Preferably, the activity (calculating with g/mmol catalyzer/hr) of catalyzer, than the same reaction height at least 20% that there is not hydrogen, is preferably up to few 50%, is preferably up to few 100%.

" productivity of catalyzer " uses the polymerizing catalyst containing Wg catalyzer (cat), can produce measuring of how many grams polymkeric substance (P) within the time period of T hour; With can be represented by the formula: P/ (TxW) and with unit gPgcat ^-1hr ^-1express.Transformation efficiency is the amount of monomer changing into polymer product, and with mol% report, and calculate with the amount of monomer be fed in reactor based on the output of polymkeric substance.The activity of catalyzer is catalyst activity how measures, and is reported as the quality (kgP/molcat) of the resulting polymer (P) that catalyzer (cat) that every mol uses is produced.

In an alternative embodiment, the activity of catalyzer is at least 50g/mmol/hr, preferably greater than or equal to 500g/mmol/hr, preferably greater than or equal to 5000g/mmol/hr, preferably greater than or equal to 50,000g/mmol/hr.In an alternative embodiment, the transformation efficiency of olefinic monomer is at least 10%, based on output and the monomer weight entered in reaction zone of polymkeric substance, preferably greater than or equal to 20%, preferably greater than or equal to 30%, preferably greater than or equal to 50%, preferably greater than or equal to 80%.

In an alternative embodiment, productivity is at least 4500g/mmol/hr, preferably greater than or equal to 5000g/mmol/hr, preferably greater than or equal to 10,000g/mmol/hr, preferably greater than or equal to 50,000g/mmol/hr.In an alternative embodiment, productivity is at least 80,000g/mmol/hr, preferably at least 150,000g/mmol/hr, preferably at least 200,000g/mmol/hr, preferably at least 250,000g/mmol/hr, preferably at least 300,000g/mmol/hr.In preferred embodiments, the productivity of the method is the polyolefine of at least 200g ethenyl blocking/mmol catalyzer/hr, preferably at least 5000g/mmol/hr, preferably at least 10,000g/mmol/hr, preferably at least 300,000g/mmol/hr.

Can such as, at typical temperature and/or pressure, 25-150 DEG C, preferred 40-120 DEG C, preferred 45-80 DEG C, and preferred 0.35-10MPa, preferred 0.45-6MPa, is preferably polymerized under preferred 0.5-4MPa.

In typical polymerization, the residence time of reaction is maximum 60 minutes, preferred 5-50 minute, preferred 10-40 minute.

In preferred embodiments, in this method, seldom or not use aikyiaiurnirsoxan beta to produce the polyolefine of ethenyl blocking.Preferably, aikyiaiurnirsoxan beta exists with 0mol%, or aikyiaiurnirsoxan beta is less than 500:1 with the mol ratio of aluminium and transition metal, is preferably less than 300:1, is preferably less than 100:1, is preferably less than 1:1 and exists.

In an alternative embodiment, if use aikyiaiurnirsoxan beta to produce the polyolefine of ethenyl blocking, then aikyiaiurnirsoxan beta is processed, the alkylaluminium cpd that removing is free, especially trimethyl aluminium.

Further, in preferred embodiments, the activator that the polyolefine producing ethenyl blocking herein uses is huge (bulky) as defined herein and is discrete (discrete).

In preferred embodiments, scavenging agent (such as trialkylaluminium) seldom or is not used to produce the polyolefine of ethenyl blocking in the method.Preferably, scavenging agent exists with 0mol%, or scavenging agent is less than 100:1 with the mol ratio of scavenging agent metal and transition metal, is preferably less than 50:1, is preferably less than 15:1, is preferably less than 10:1 and exists.

In preferred embodiments, seldom or not use scavenging agent to produce the polymkeric substance of ethenyl blocking in the method.Preferably, scavenging agent (such as trialkylaluminium) exists with 0mol%, or scavenging agent is less than 100:1 with the mol ratio of scavenging agent metal and transition metal, is preferably less than 50:1, is preferably less than 15:1, is preferably less than 10:1 and exists.

In preferred embodiments, be polymerized under the following conditions: 1) at the temperature of 0-300 DEG C under (preferred 25-150 DEG C, preferred 40-120 DEG C, preferred 45-80 DEG C); 2) under the pressure of normal atmosphere to 10MPa (preferred 0.35-10MPa, preferred 0.45-6MPa, preferred 0.5-4MPa); 3) (such as Trimethylmethane, butane, pentane, iso-pentane, hexane class, isohexane, heptane, octane, dodecane and composition thereof in aliphatic hydrocarbon solvent; Ring-type and clicyclic hydrocarbon, such as hexanaphthene, suberane, methylcyclohexane, methylcycloheptane, and composition thereof; Preferred wherein aromatic hydrocarbons to be less than 1wt%, preferably with 0.5wt%, preferably exists with 0wt%, the weight based on solvent in solvent); 4) catalyst system wherein used in polymerization comprises and is less than 0.5mol%, preferred 0mol% aikyiaiurnirsoxan beta, or aikyiaiurnirsoxan beta is less than 500:1 with the mol ratio of aluminium and transition metal, is preferably less than 300:1, is preferably less than 100:1, is preferably less than 1:1 and exists; 5) be polymerized in a reaction zone; 6) productivity of catalyst compound be at least 80,000g/mmol/hr (preferably at least 150,000g/mmol/hr, preferably at least 200,000g/mmol/hr, preferably at least 250,000g/mmol/hr, preferably at least 300,000g/mmol/hr); 7) optionally, there is not scavenging agent (such as trialkyl aluminium compound) (such as, to exist with 0mol%, or scavenging agent is less than 100:1 with the mol ratio of scavenging agent metal and transition metal, preferably be less than 50:1, be preferably less than 15:1, be preferably less than 10:1 and exist); With 8) in polymerization reactor, there is the hydrogen that dividing potential drop is 0.001-50psig (0.007-345kPa) (preferred 0.01-25psig (0.07-172kPa), more preferably 0.1-10psig (0.7-70kPa)).In preferred embodiments, the catalyst system used in polymerization comprises just a kind of catalyst compound." reaction zone " is the container wherein occurring to be polymerized also referred to as " polymeric area ", such as batch reactor.When with or series connection or the structure of parallel connection use multiple reactor time, each reactor is regarded as independently polymeric area.For the multi-stage polymeric in both batch reactor and flow reactor, each polymeric segment is regarded as independently polymeric area.In preferred embodiments, be polymerized in a reaction zone.Room temperature is 23 DEG C, except as otherwise noted.

Manufacture the polyolefinic catalyst compound/system of ethenyl blocking

" catalyst system " is at least one catalyst compound, at least one activator, optional coactivator, and the binding substances of optional solid support material, and wherein this system can make monomer polymerization become polymkeric substance.For the object of the present invention and claims, when catalyst system is described to the neutral stable form containing each component, it will be understood by those skilled in the art that the ionic species of this component produces the form of polymkeric substance by with monomer reaction.

In specification sheets herein, metallocene catalyst can be described to catalyst precursor, pre-catalyst compound, or transistion metal compound, and these terms are used interchangeably." anion ligand " be contribution a pair or more to electronics to the part of the bear electricity of metal ion." neutral donor part " be contribution a pair or more to electronics to the electroneutral part of metal ion.

Metallocene catalyst is defined as the organometallic compound of the cyclopentadienyl moieties (or replace cyclopentadienyl moieties) with at least one π-bonding and the more commonly cyclopentadienyl moieties of two π-bondings or the cyclopentadienyl moieties of replacement.It comprises the part of other π-bondings, such as indenyl or fluorenyl or derivatives thereof.

The catalyst compound that polyolefinic this paper of production ethenyl blocking is useful comprises the one or more of metallocene compounds represented with following formula:

Wherein:

Hf is hafnium;

Each X independently selected from the alkyl with 1-20 carbon atom, hydrogen (hydride), amino, alkoxyl group, sulfenyl, phosphorus base, halogen, diolefine, amine, phosphine, ether or its binding substances, preferable methyl, ethyl, propyl group, butyl, phenyl, benzyl, muriate, bromide, iodide, (or two X can form a part for condensed ring or member ring systems);

Each Q is carbon or heteroatoms independently, preferred C, N, (preferably at least one Q is heteroatoms, or at least two Q are identical or different heteroatomss for P, S, or at least three Q are identical or different heteroatomss, or at least four Q are identical or different heteroatomss);

Each R ¹be hydrogen or C independently ₁-C ₈alkyl, preferred C ₁-C ₈straight chained alkyl, preferable methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, or octyl group, R ¹can with R ²identical or different;

Each R ²be hydrogen or C independently ₁-C ₈alkyl, preferred C ₁-C ₈straight chained alkyl, preferable methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, or octyl group, condition is R ¹or R ²in at least one be not hydrogen, preferred R ¹and R ²the two is not all hydrogen, preferred R ¹and/or R ²there is no branching;

Each R ³be hydrogen independently, or there is 1-8 carbon atom, the substituted or unsubstituted alkyl of a preferred 1-6 carbon atom, preferred substituted or unsubstituted C ₁-C ₈straight chained alkyl, preferable methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, but condition is at least three R ³not hydrogen (or four R ³base is not hydrogen, or 5 R ³base is not hydrogen); Or, when using this catalyst compound to manufacture homopolymer, each R ³be hydrogen independently, or there is 1-8 carbon atom, the substituted or unsubstituted alkyl of a preferred 1-6 carbon atom, preferred substituted or unsubstituted C ₁-C ₈straight chained alkyl, preferable methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, but condition is: 1) all 5 R ³base is methyl; Or 2) four R ³base is not hydrogen and at least one R ³base is C ₂-C ₈substituted or unsubstituted alkyl (preferably at least two, three, four or five R ³base is C ₂-C ₈substituted or unsubstituted alkyl) };

Each R ⁴be hydrogen independently, or substituted or unsubstituted alkyl, heteroatoms or containing heteroatomic group, preferably has 1-20 carbon atom, the substituted or unsubstituted alkyl of a preferred 1-8 carbon atom, preferred substituted or unsubstituted C ₁-C ₈straight chained alkyl, preferable methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, substituted-phenyl (such as propyl group phenyl), phenyl, silyl, replaces silyl (such as, CH ₂siR', wherein R' is C ₁-C ₁₂alkyl, such as methyl, ethyl, propyl group, butyl, phenyl);

R ⁵hydrogen, or C ₁-C ₈alkyl, preferred C ₁-C ₈straight chained alkyl, preferable methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, or octyl group;

R ⁶hydrogen, or C ₁-C ₈alkyl, preferred C ₁-C ₈straight chained alkyl, preferable methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, or octyl group;

Each R ⁷be hydrogen independently, or C ₁-C ₈alkyl, preferred C ₁-C ₈straight chained alkyl, preferable methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, or octyl group; Condition is at least 7 R ⁷base is not hydrogen, or at least 8 R ⁷base is not hydrogen, or all R ⁷base is not hydrogen, (the R on 3 and 4 preferably on each Cp ring of formula IV ⁷base is not hydrogen);

N is nitrogen;

R ₂ ^at is bridge, and preferred T is Si or Ge, preferred Si, and each R ^abe hydrogen independently, or halogen or C ₁-C ₂₀alkyl, such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, phenyl, benzyl, substituted-phenyl, and two R ^acan be formed containing aromatics, fractional saturation, or the ring texture of saturated ring-type or fused ring system; Be that any two adjacent R bases can form condensed ring or multicenter fused ring system with further condition, wherein these rings can be aromatic hydrocarbons, fractional saturation or saturated.

In an alternative embodiment, at least one R ⁴base is not hydrogen, or at least two R ⁴base is not hydrogen, or at least three R ⁴base is not hydrogen, or at least four R ⁴base is not hydrogen, or all R ⁴base is not hydrogen.

The catalyst compound be particularly useful in the present invention comprise following in one or more:

(1,3-dimethylindenyl) (pentamethylcyclopentadiene base) dimethyl closes hafnium,

(1,3,4,7-tetramethylindenyl) (pentamethylcyclopentadiene base) dimethyl closes hafnium,

(1,3-dimethylindenyl) (tetramethyl-ring pentadienyl) dimethyl closes hafnium,

(1,3-diethyl indenyl) (pentamethylcyclopentadiene base) dimethyl closes hafnium,

(1,3-dipropyl indenyl) (pentamethylcyclopentadiene base) dimethyl closes hafnium,

(1-methyl-3-propyl group indenyl) (pentamethylcyclopentadiene base) dimethyl closes hafnium,

(1,3-dimethylindenyl) (tetramethyl-propyl-cyclopentadienyl) dimethyl closes hafnium,

(1,2,3-trimethylindenyl) (pentamethylcyclopentadiene base) dimethyl closes hafnium,

(1,3-dimethylbiphenyl indenyl) (pentamethylcyclopentadiene base) dimethyl closes hafnium,

(2,7-dual-tert-butyl fluorenyl) (pentamethylcyclopentadiene base) dimethyl closes hafnium,

(9-methylfluorenyl) (pentamethylcyclopentadiene base) dimethyl closes hafnium,

(2,7,9-trimethylammonium fluorenyl) (pentamethylcyclopentadiene base) dimethyl closes hafnium,

μ-dihydro silyl-bis-(tetramethyl-ring pentadienyl) dimethyl closes hafnium,

μ-dimetylsilyl (tetramethyl-ring pentadienyl) (3-oxypropyl trimethyl cyclopentadienyl) dimethyl closes hafnium,

μ-Bicyclopropyl silyl (bis-tetramethyl cyclopentadienyl) dimethyl closes hafnium,

In an alternative embodiment, " dimethyl " in the enumerating of above-mentioned catalyst compound after transition metal by dihalo-root (such as, dichloro root, dibromo root or difluoro root) or the replacement of biphenol compound, when especially using together with alumoxane activator.

The useful preferred active agent used together with above-mentioned comprises:

Dimethylanalsniurn four (pentafluorophenyl group) borate, dimethylanalsniurn four (seven fluoronaphthalene bases) borate, trimethyl ammonium four (perfluorinated biphenyl) borate, triethyl ammonium four (perfluorinated biphenyl) borate, tripropyl ammonium four (perfluorinated biphenyl) borate, three (normal-butyl) ammonium four (perfluorinated biphenyl) borate, three (tertiary butyl) ammonium four (perfluorinated biphenyl) borate, N, accelerine ion four (perfluorinated biphenyl) borate, N, N-Diethyl Aniline ion four (perfluorinated biphenyl) borate, N, N-dimethyl-(2, 4, 6-trimethylaniline ion) four (perfluorinated biphenyl) borate, (tropillium) four (perfluorinated biphenyl) borate, triphenyl carbon cation four (perfluorinated biphenyl) borate, triphenyl phosphonium four (perfluorinated biphenyl) borate, triethylsilyl (silylium) four (perfluorinated biphenyl) borate, benzene (diazonium) four (perfluorinated biphenyl) borate, and [the 4-tertiary butyl-PhNMe ₂h] [(C ₆f ₃(C ₆f ₅) ₂) ₄b] (wherein Ph is phenyl and Me is methyl).

In another embodiment, the catalyst compound that following formula represents can be used, produce the polyolefine of useful ethenyl blocking herein:

Wherein M is hafnium or zirconium (preferred hafnium); Each X is independently selected from the alkyl with 1-20 carbon atom, and hydrogen, amino, alkoxyl group, sulfenyl, phosphorus base, halogen root, diolefine, amine, phosphine, ether, and combination, (two X can form condensed ring or member ring systems) (preferably each X is independently selected from halogen root and C ₁-C ₅alkyl, preferably each X is methyl); Each R ⁸be C independently ₁-C ₁₀alkyl (preferable methyl, ethyl, propyl group, butyl, amyl group, hexyl, or its isomer, preferably each R ⁸methyl); Each R ⁹be C independently ₁-C ₁₀alkyl (preferable methyl, ethyl, propyl group, butyl, amyl group, hexyl, or its isomer, preferably each R ⁹n-propyl); Each R ¹⁰hydrogen; Each R ¹¹, R ¹²and R ¹³be hydrogen or substituted or unsubstituted alkyl independently, heteroatoms or containing heteroatomic group (preferred hydrogen); T is bridged group (preferred T is dialkyl group silicon or dialkyl Germanium, and preferred T is dimethyl-silicon); Any adjacent R with further condition ¹¹, R ¹²and R ¹³base can form condensed ring or multicenter fused ring system, and wherein this ring can be aromatic hydrocarbons, fractional saturation or saturated.About this catalyst compound and the further information of macromolecular purposes manufacturing ethenyl blocking thereof, refer to the co-applications USSN13/072280 that the title submitted on March 25th, 2011 be " using method of the polymkeric substance of new catalyst and production ethenyl blocking thereof ".

Especially catalyst compound used in the present invention comprise following in one or more of:

Two (2-methyl-3-propyl group indenyl) dimethyl of rac-dimetylsilyl closes hafnium,

Two (2-methyl-3-propyl group indenyl) dimethyl of rac-dimetylsilyl closes zirconium,

Two (2-ethyl-3-propyl group indenyl) dimethyl of rac-dimetylsilyl closes hafnium,

Two (2-ethyl-3-propyl group indenyl) dimethyl of rac-dimetylsilyl closes zirconium,

Two (2-methyl-3-ethyl-indenyl) dimethyl of rac-dimetylsilyl closes hafnium,

Two (2-methyl-3-ethyl-indenyl) dimethyl of rac-dimetylsilyl closes zirconium,

Two (2-methyl-3-isopropylindenyl) dimethyl of rac-dimetylsilyl closes hafnium,

Two (2-methyl-3-isopropylindenyl) dimethyl of rac-dimetylsilyl closes zirconium,

Two (2-methyl-3-butyl indenyl) dimethyl of rac-dimetylsilyl closes hafnium,

Two (2-methyl-3-butyl indenyl) dimethyl of rac-dimetylsilyl closes zirconium,

Two (2-methyl-3-propyl group indenyl) dimethyl of rac-dimethyl germyl closes hafnium,

Two (2-methyl-3-propyl group indenyl) dimethyl of rac-dimethyl germyl closes zirconium,

Two (2-ethyl-3-propyl group indenyl) dimethyl of rac-dimethyl germyl closes hafnium,

Two (2-ethyl-3-propyl group indenyl) dimethyl of rac-dimethyl germyl closes zirconium,

Two (2-methyl-3-ethyl-indenyl) dimethyl of rac-dimethyl germyl closes hafnium,

Two (2-methyl-3-ethyl-indenyl) dimethyl of rac-dimethyl germyl closes zirconium,

Two (2-methyl-3-isopropylindenyl) dimethyl of rac-dimethyl germyl closes hafnium,

Two (2-methyl-3-isopropylindenyl) dimethyl of rac-dimethyl germyl closes zirconium,

Two (2-methyl-3-butyl indenyl) dimethyl of rac-dimethyl germyl closes hafnium,

Two (2-propyl group-3-methylindenyl) dimethyl of rac-dimetylsilyl closes hafnium,

Two (2-propyl group-3-methylindenyl) dimethyl of rac-dimetylsilyl closes zirconium,

Two (2-propyl group-3-ethyl-indenyl) dimethyl of rac-dimetylsilyl closes hafnium,

Two (2-propyl group-3-ethyl-indenyl) dimethyl of rac-dimetylsilyl closes zirconium,

Two (2-propyl group-3-butyl indenyl) dimethyl of rac-dimetylsilyl closes hafnium,

Two (2-propyl group-3-butyl indenyl) dimethyl of rac-dimetylsilyl closes zirconium,

Two (2-methyl-3-butyl indenyl) dimethyl of rac-dimetylsilyl closes hafnium,

Two (2-methyl-3-butyl indenyl) dimethyl of rac-dimetylsilyl closes zirconium,

Two (2, the 3-dimethyl) dimethyl of rac-dimetylsilyl closes hafnium,

Two (2, the 3-dimethyl) dimethyl of rac-dimetylsilyl closes zirconium,

Two (2-propyl group-3-methylindenyl) dimethyl of rac-dimethyl germyl closes hafnium,

Two (2-propyl group-3-methylindenyl) dimethyl of rac-dimethyl germyl closes zirconium,

Two (2-propyl group-3-ethyl-indenyl) dimethyl of rac-dimethyl germyl closes hafnium,

Two (2-propyl group-3-ethyl-indenyl) dimethyl of rac-dimethyl germyl closes zirconium,

Two (2-propyl group-3-butyl indenyl) dimethyl of rac-dimethyl germyl closes hafnium,

Two (2-propyl group-3-butyl indenyl) dimethyl of rac-dimethyl germyl closes zirconium,

Two (2-methyl-3-butyl indenyl) dimethyl of rac-dimethyl germyl closes hafnium,

Two (2-methyl-3-butyl indenyl) dimethyl of rac-dimethyl germyl closes zirconium,

Two (2, the 3-dimethyl) dimethyl of rac-dimethyl germyl closes hafnium, and

Two (2, the 3-dimethyl) dimethyl of rac-dimethyl germyl closes zirconium,

In an alternative embodiment, " dimethyl " in the enumerating of above-mentioned catalyst compound after transition metal by dihalo-root (such as, dichloride or difluoride) or the replacement of biphenol compound, when especially using together with alumoxane activator.

In special embodiment, catalyst compound is that two (2-methyl-3-propyl group indenyl) dimethyl of rac-dimetylsilyl closes hafnium or dichloride, or two (2-methyl-3-propyl group indenyl) dimethyl of rac-dimetylsilyl closes zirconium or dichloride.

The useful preferred active agent used together with above-mentioned comprises:

Dimethylanalsniurn four (pentafluorophenyl group) borate, dimethylanalsniurn four (seven fluoronaphthalene bases) borate, trimethyl ammonium four (perfluorinated biphenyl) borate, triethyl ammonium four (perfluorinated biphenyl) borate, tripropyl ammonium four (perfluorinated biphenyl) borate, three (normal-butyl) ammonium four (perfluorinated biphenyl) borate, three (tertiary butyl) ammonium four (perfluorinated biphenyl) borate, N, accelerine ion four (perfluorinated biphenyl) borate, N, N-Diethyl Aniline ion four (perfluorinated biphenyl) borate, N, N-dimethyl-(2, 4, 6-trimethylaniline ion) four (perfluorinated biphenyl) borate, four (perfluorinated biphenyl) borate, triphenyl carbon cation four (perfluorinated biphenyl) borate, triphenyl phosphonium four (perfluorinated biphenyl) borate, triethylsilyl (silylium) four (perfluorinated biphenyl) borate, benzene (diazonium) four (perfluorinated biphenyl) borate, and [the 4-tertiary butyl-PhNMe ₂h] [(C ₆f ₃(C ₆f ₅) ₂) ₄b] (wherein Ph is phenyl and Me is methyl).

The preferably combination of catalyzer and activator comprises: N, accelerine ion four (perfluorinated biphenyl) borate and two (2-methyl-3-propyl group indenyl) dimethyl of rac-dimetylsilyl close hafnium, or two (2-methyl-3-propyl group indenyl) dimethyl of rac-dimetylsilyl closes zirconium.

Wherein M is hafnium or zirconium; Each X independently selected from the alkyl with 1-20 carbon atom, hydrogen, amino, alkoxyl group, sulfenyl, phosphorus base, halogen, diolefine, amine, phosphine, ether, and combination, R ¹⁵and R ¹⁷be C independently of one another ₁-C ₈alkyl (preferred C ₁-C ₈straight chained alkyl, preferable methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or octyl group); R ¹⁶, R ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²², R ²³, R ²⁴, R ²⁵, R ²⁶, R ²⁷and R ²⁸be hydrogen or replacement or unsubstituting hydrocarbyl (a preferred 1-6 carbon atom, the preferred substituted or unsubstituted C with 1-8 carbon atom independently of one another ₁-C ₈straight chained alkyl, preferable methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group).In preferred embodiments, R ²⁴-R ²⁸in at least three be not hydrogen (or R ²⁴-R ²⁸in four be not hydrogen, or R ²⁴-R ²⁸in five be not hydrogen).In preferred embodiments, R ²⁴-R ²⁸in all five groups are methyl.In preferred embodiments, R ²⁴-R ²⁸four in base is not hydrogen, and R ²⁴-R ²⁸in at least one be C ₂-C ₈substituted or unsubstituted alkyl (preferred R ²⁴-R ²⁸at least two in base, three, four, or five is C ₂-C ₈substituted or unsubstituted alkyl).In another preferred embodiment, R ¹⁵and R ¹⁷methyl, R ¹⁶hydrogen, R ¹⁸-R ²³all hydrogen, R ²⁴-R ²⁸be all methyl, and each X is methyl.About this catalyst compound and the further information of macromolecular purposes manufacturing ethenyl blocking thereof, refer to the co-applications USSN13/072279 that the title submitted on March 25th, 2011 is " for the production of the propylene of ethenyl blocking and the catalyst performance of the macromolecular raising of ethylene/propene ".

The catalyst compound be particularly useful in the present invention comprises (CpMe ₅) (1,3-Me ₂benzo [e] indenyl) HfMe ₂, (CpMe ₅) (1-methyl-3-n-propyl benzo [e] indenyl) HfMe ₂, (CpMe ₅) (1-n-propyl-3-methyl benzo [e] indenyl) HfMe ₂, (CpMe ₅) (1-methyl-3-normal-butyl benzo [e] indenyl) HfMe ₂, (CpMe ₅) (1-normal-butyl-3-methyl benzo [e] indenyl) HfMe ₂, (CpMe ₅) (1-ethyl-3-methyl benzo [e] indenyl) HfMe ₂, (CpMe ₅) (1-methyl-3-ethyl benzo [e] indenyl) HfMe ₂, (CpMe ₄n-propyl) (1,3-Me ₂benzo [e] indenyl) HfMe ₂, (CpMe ₄n-propyl) (1-methyl-3-n-propyl benzo [e] indenyl) HfMe ₂, (CpMe ₄n-propyl) (1-n-propyl-3-methyl benzo [e] indenyl) HfMe ₂, (CpMe ₄n-propyl) (1-methyl-3-normal-butyl benzo [e] indenyl) HfMe ₂, (CpMe ₄n-propyl) (1-normal-butyl-3-methyl benzo [e] indenyl) HfMe ₂, (CpMe ₄n-propyl) (1-ethyl-3-methyl benzo [e] indenyl) HfMe ₂, (CpMe ₄n-propyl) (1-methyl-3-ethyl benzo [e] indenyl) HfMe ₂, (CpMe ₄normal-butyl) (1,3-Me ₂benzo [e] indenyl) HfMe ₂, (CpMe ₄normal-butyl) (1-methyl 3-n-propyl benzo [e] indenyl) HfMe ₂, (CpMe ₄normal-butyl) (1-n-propyl-3-methyl benzo [e] indenyl) HfMe ₂, (CpMe ₄normal-butyl) (1-methyl-3-normal-butyl benzo [e] indenyl) HfMe ₂, (CpMe ₄normal-butyl) (1-normal-butyl-3-methyl benzo [e] indenyl) HfMe ₂, (CpMe ₄normal-butyl) (1-ethyl-3-methyl benzo [e] indenyl) HfMe ₂, (CpMe ₄normal-butyl) (1-methyl-3-ethyl benzo [e] indenyl) HfMe ₂, and the homologue of zirconium.

In an alternative embodiment, " the dimethyl " (Me in the enumerating of above-mentioned catalyst compound after transition metal ₂) replaced, when especially using together with alumoxane activator by dihalo-root (such as, dichloro root or difluoro root) or biphenol compound.

The useful preferred active agent used together with above-mentioned comprises:

Dimethylanalsniurn four (pentafluorophenyl group) borate, dimethylanalsniurn four (seven fluoronaphthalene bases) borate, trimethyl ammonium four (perfluorinated biphenyl) borate, triethyl ammonium four (perfluorinated biphenyl) borate, tripropyl ammonium four (perfluorinated biphenyl) borate, three (normal-butyl) ammonium four (perfluorinated biphenyl) borate, three (tertiary butyl) ammonium four (perfluorinated biphenyl) borate, N, N-Diethyl Aniline ion four (perfluorinated biphenyl) borate, N, N-dimethyl-(2, 4, 6-trimethylaniline ion) four (perfluorinated biphenyl) borate, four (perfluorinated biphenyl) borate, triphenyl carbon cation four (perfluorinated biphenyl) borate, triphenyl phosphonium four (perfluorinated biphenyl) borate, triethylsilyl (silylium) four (perfluorinated biphenyl) borate, benzene (diazonium) four (perfluorinated biphenyl) borate, and [the 4-tertiary butyl-PhNMe ₂h] [(C ₆f ₃(C ₆f ₅) ₂) ₄b].

In preferred embodiments, the title can submitted to as on March 25th, 2011, for described in the co-applications USSN61/467681 of " BranchedVinylTerminatedPolymersandMethodsforProductionTh ereof (polymkeric substance of branched ethylene base end-blocking and production method thereof) ", produces branched chain polymer described herein.

About above-mentioned catalyst compound, term " replacement " refers to that hydrogen base is by alkyl, heteroatoms or replace containing heteroatomic group.Such as, the ethyl that replaced by-OH base by methyl substituted Cp base and ethanol of methyl cyclopentadiene (Cp).

The activation method of activator and catalyst compound, to manufacture the polymkeric substance of ethenyl blocking

Term " promotor " and " activator " are used interchangeably, and to be defined as be become catalytic activity catalyst compound positively charged ion by transforming neutral catalyst compound, thus activate any compound of above-described any one catalyst compound.Indefiniteness activator such as comprises aikyiaiurnirsoxan beta, aluminum alkyls, ionization activator (they can be neutral or ion), and the promotor of routine-type.Preferred activator typically comprises aluminium alkoxide compound, modified alumoxane compounds, (it extracts the metal ligand of the reactive σ-bonding of (abstract) with ionization anion pre-cursor compounds, thus produce metal complex positively charged ion, and provide non-coordinated or the weakly coordinating anion of electric charge-balance).

In one embodiment, alumoxane activator is used as the activator in this catalyst composition.Aikyiaiurnirsoxan beta is normally containing-Al (R ¹) polymer compound of-O-subelement, wherein R ¹it is alkyl.The example of aikyiaiurnirsoxan beta comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane and isobutyl aluminium alkoxide.The alkylaluminoxane of alkylaluminoxane and modification is suitable as catalyst activator, and especially when extractible part is alkyl, halogen root, when alkoxyl group or amino.Also the mixture of different aikyiaiurnirsoxan beta and modified alumoxane can be used.Preferably can use visual transparent methylaluminoxane.The aikyiaiurnirsoxan beta of muddiness or gelling can be filtered, produce clear solution or can decantation is transparent from turbid solution aikyiaiurnirsoxan beta.Another aikyiaiurnirsoxan beta is methylaluminoxane (MMAO) promotor (be available commercially from AkzoChemicals with trade(brand)name ModifiedMethylalumoxanetype3A, covered by patent No. U.S. Patent No. 5041584) of the modification of 3A type.

When activator is aikyiaiurnirsoxan beta (modification or unmodified), some embodiments select the maximum activation dosage (relative to metal catalytic site) of excessive 5000 moles times of Al/M on catalyst precursor.Minimum activator is 1:1 mol ratio with the ratio of catalyst precursor.The preferable range substituted comprises maximum 500:1, or maximum 200:1, or maximum 100:1, or 1:1 to 50:1.

{ 00198} in preferred embodiments, in the method seldom or be not suitable for aikyiaiurnirsoxan beta to produce the polyolefine of ethenyl blocking.Preferably, aikyiaiurnirsoxan beta exists with 0mol%, or aikyiaiurnirsoxan beta is less than 500:1 with the mol ratio of aluminium and transition metal, is preferably less than 300:1, is preferably less than 100:1, is preferably less than 1:1 and exists.

In an alternative embodiment, if use aikyiaiurnirsoxan beta to produce VTM, then process aikyiaiurnirsoxan beta, to remove free alkylaluminium cpd, especially trimethyl aluminium.

Further, in preferred embodiments, the activator that the polyolefine producing ethenyl blocking herein uses is huge as defined herein and is discrete.

The aluminum alkyls or the organic radical aluminum compound that can be used as activator promotor (or scavenging agent) comprise trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium and analogue.

Ionization activator

It is within the scope of the invention that use ionization or stoichiometric activator, the non-coordinating anion of neutral or ion (as in the USSN12/143663 that on June 20th, 2008 submits to define), such as three (normal-butyl) ammonium four (pentafluorophenyl group) borate, three perfluorophenyl boron metalloid precursors or three perfluoronapthyl boron metalloid precursors, poly-halogenation is mixed borane anion (WO98/43983), boric acid (U.S. Patent No. 5942459), or its binding substances.Same it is within the scope of the invention that, separately or be combined neutrality or ion activation agent with aikyiaiurnirsoxan beta or modified alumoxane activators.Preferred active agent is N, accelerine ion four (perfluoronapthyl) borate, N, accelerine ion four (perfluorinated biphenyl) borate, N, accelerine ion four (3, two (trifluoromethyl) phenyl of 5-) borate, triphenyl carbon cation four (perfluoronapthyl) borate, triphenyl carbon cation four (perfluorinated biphenyl) borate, triphenyl carbon cation four (two (trifluoromethyl) phenyl of 3,5-) borate, or triphenyl carbon cation four (perfluorophenyl) borate.About useful activator, refer to the USSN12/143663 submitted on June 20th, 2008 herein.

In another embodiment, activator is the huge activator represented with following formula:

Wherein:

Each R ₁be halogen root independently, preferred fluorine root;

Each R ₂be halogen root independently, C ₆-C ₂₀substituted arene base or chemical formula are-O-Si-R _asiloxy-, wherein R _ac ₁-C ₂₀alkyl or hy drocarbylsilyl (preferred R ₂fluorochemical or perfluorinated phenyl group);

Each R ₃halogen root, C ₆-C ₂₀substituted arene base or chemical formula are-O-Si-R _asiloxy-, wherein R _ac ₁-C ₂₀alkyl or hy drocarbylsilyl (preferred R ₃fluorochemical or C ₆perfluorinated arene base); Wherein R ₂and R ₃can be formed one or more saturated or unsaturated, substituted or unsubstituted ring (preferred R ₂and R ₃form perfluorination phenyl ring);

L is neutral Lewis base;

(L-H) ⁺it is Bronsted acid;

D is 1,2 or 3;

Wherein the molecular weight of negatively charged ion is greater than 1020g/mol; With

At least three in substituting group wherein on B atom respective molecular volumes are greater than 250 cubic angstroms, or are greater than 300 cubic angstroms, or or are greater than 500 cubic angstroms.

Use " molecular volume " being similar to as the sterically hindered volume of activator molecule in solution herein.The substituting group relatively with differing molecular volume makes compared with the substituting group had compared with macromole volume, has and is regarded as " so not huge " compared with the substituting group of small molecules volume.On the contrary, compared with the substituting group had compared with small molecules volume, have and can be regarded as " huger " compared with the substituting group of macromole volume.

Can as " ASimple " BackoftheEnvelope " MethodforEstimatingtheDensitiesandMolecularVolumesofLiqu idsandSolids; " JournalofChemicalEducation, 71st volume, o. 11th, in November, 1994, report in 962-964 page, calculate molecular volume.Use following formula: MV=8.3V _s, calculate molecular volume (MV), cubic unit dust, wherein V _sit is (scaled) volume that converts.V _sbe the relative volume sum of constituting atom, and use the relative volume of following table, calculate according to substituent molecular formula.For condensed ring, for each condensed ring, V _sdecline 7.5%.

Element	Relative volume
		H	1
First short period, Li to F	2
		Second short period, Na to Cl	4
First long period, K to Br	5
		Second long period, Rb to I	7.5
3rd long period, Cs to Bi	9

The bulky substituent that exemplifies in the activator be applicable to herein and their respective conversion volumes and molecular volume have been shown in following table.Dotted line key represents and is bonded on boron, as general formula above.

The huge activator exemplified that can be used for catalyst system herein comprises: trimethyl ammonium four (perfluoronapthyl) borate, triethyl ammonium four (perfluoronapthyl) borate, tripropyl ammonium four (perfluoronapthyl) borate, three (normal-butyl) ammonium four (perfluoronapthyl) borate, three (tertiary butyl) ammonium four (perfluoronapthyl) borate, N, accelerine ion four (perfluoronapthyl) borate, N, N-Diethyl Aniline ion four (perfluoronapthyl) borate, N, N-dimethyl-(2, 4, 6-trimethylaniline ion) four (perfluoronapthyl) borate, four (perfluoronapthyl) borate, triphenyl carbon cation four (perfluoronapthyl) borate, triphenyl phosphonium four (perfluoronapthyl) borate, triethylsilyl (silylium) four (perfluoronapthyl) borate, benzene (diazonium) four (perfluoronapthyl) borate, trimethyl ammonium four (perfluorinated biphenyl) borate, triethyl ammonium four (perfluorinated biphenyl) borate, tripropyl ammonium four (perfluorinated biphenyl) borate, three (normal-butyl) ammonium four (perfluorinated biphenyl) borate, three (tertiary butyl) ammonium four (perfluorinated biphenyl) borate, N, accelerine ion four (perfluorinated biphenyl) borate, N, N-Diethyl Aniline ion four (perfluorinated biphenyl) borate, N, N-dimethyl-(2, 4, 6-trimethylaniline ion) four (perfluorinated biphenyl) borate, four (perfluorinated biphenyl) borate, triphenyl carbon cation four (perfluorinated biphenyl) borate, triphenyl phosphonium four (perfluorinated biphenyl) borate, triethylsilyl (silylium) four (perfluorinated biphenyl) borate, benzene (diazonium) four (perfluorinated biphenyl) borate, and [the 4-tertiary butyl-PhNMe ₂h] [(C ₆f ₃(C ₆f ₅) ₂) ₄b] and U.S. Patent No. 7297653 disclosed in type.

For non-alumoxane activator, typical activator is 1:1 mol ratio with the ratio of catalyst precursor.The preferable range substituted comprises 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to 500:1, or 1:1 to 1000:1.The scope be particularly useful is 0.5:1 to 10:1, preferred 1:1 to 5:1.

The binding substances of activator

It is within the scope of the invention that can combined catalyst compound and above-described one or more of activator or activation method.Such as, at United States Patent(USP) Nos. 5153157,5453410, in European publication EP0573120B1, PCT application WO94/07928 and WO95/14044, describe the binding substances of activator.These documents all discuss and ionize activator and be combined aikyiaiurnirsoxan beta.

Solid support material

In embodiment herein, catalyst system can comprise inert support material.Preferably, the material of load is porous carrier materials, such as talcum, and inorganic oxide.Other solid support materials comprise zeolite, clay, organic clay, or any other organic or inorganic solid support material and analogue, or its mixture.

Preferably, solid support material is the inorganic oxide of particulate form.The suitable inorganic oxide material used in metallocene catalyst system herein comprises the 2nd, the metal oxide of 4,13 and 14 races, such as silicon oxide, aluminum oxide and composition thereof.Can separately or other inorganic oxides be combined with silicon oxide or aluminum oxide be magnesium oxide, titanium oxide, zirconium white, and analogue.But, other suitable solid support materials can be used, such as fine functionalised polyolefin, such as fine polyethylene.The carrier be particularly useful comprises magnesium oxide, titanium oxide, zirconium white, montmorillonite, phyllosilicate, zeolite, talcum, clay, and analogue.In addition, the binding substances of these solid support materials can be used, such as silicon oxide-chromium, silica-alumina, silica-titania, and analogue.Preferred solid support material comprises Al ₂o ₃, ZrO ₂, SiO ₂, and binding substances, more preferably SiO ₂, Al ₂o ₃, or SiO ₂/ Al ₂o ₃.

Preferably, solid support material, most preferably the surface area of inorganic oxide is that about 10-is about 700m ²/ g, pore volume scope is about 4.0cc/g for about 0.1-, and mean particle size range is about 5-about 500 microns.More preferably, the surface area of solid support material is about 500m for about 50- ²/ g, pore volume scope is about 3.5cc/g for about 0.5-, and mean particle size range is about 10-about 200 microns.Most preferably the surface area of solid support material is about 400m for about 100- ²/ g, pore volume scope is about 3.0cc/g for about 0.8-, and mean particle size range is about 5-about 100 microns.The average cell size scope of solid support material used in the present invention is 10-1000 dust, preferred 50-about 500 dust, more preferably 75-about 350 dust.In some embodiments, solid support material is the amorphous silicon oxide (surface-area=300m of high surface area ²/ gm, pore volume is 1.65cm ³/ gm), the example is commercially available by DavisonChemicalDivisionofW.R.GraceandCompany with trade(brand)name DAVISON952 or DAVISON955.In other embodiments, DAVISON948 is used.

Solid support material should be dry, that is do not have the water of absorption.By about 100 DEG C of-Yue 1000 DEG C, preferably heat or calcining at 600 DEG C, carry out the drying of solid support material.When solid support material is silicon oxide, heat it at least 200 DEG C, preferably about 200 DEG C of-Yue 850 DEG C, and most preferably from about 600 DEG C; With through about 1 minute-Yue 100 hours, about 12 hours-Yue 72 hours, or about 24 hours-Yue time of 60 hours.Burnt solid support material must have at least some reactive hydroxyl (OH), to produce catalyst system of the present invention.Then burnt solid support material is made to contact with at least one polymerizing catalyst of activator with containing at least one metallocene compound.

Manufacture the method for the catalyst system of load

Slurried in non-polar solvent have reactive surfaces group, the typically solid support material of hydroxyl, and gained slurry is contacted with the solution of activator with metallocene compound.By being incorporated in solvent by solid support material, and heating to about 0 to about 70 DEG C, this mixture, preferably arriving about 25 to about 60 DEG C, preferably at room temperature, preparing the slurry of solid support material in solvent.Duration of contact, scope typically was about 0.5 hour to 24 hours, about 0.5 hour to about 8 hours, or about 0.5 hour to about 4 hours.

Suitable non-polar solvent is wherein all reactants used herein, i.e. activator, and metallocene compound is solvable at least partly within it and be the material of liquid at the reaction temperatures.Preferred non-polar solvent is alkane, such as iso-pentane, hexane, normal heptane, octane, nonane and decane, although other materials various also can be used, comprising naphthenic hydrocarbon, and such as hexanaphthene, aromatic hydrocarbons, such as benzene, toluene and ethylbenzene.

In embodiment herein, solid support material is contacted with the solution of activator with metallocene compound, so that titration reactive group on a support material, form the polymerizing catalyst of load.Metallocene compound, between activator and solid support material duration of contact section with the same length needed for the reactive group on titration solid support material." titration (titrate) " refers to and obtainable reaction-ity group reaction in surfaces of carrier materials, thus reduces surface hydroxyl at least 80%, at least 90%, at least 95% or at least 98%.Based on the type of calcining temperature with the solid support material used, the concentration of surface reaction group can be determined.Calcining temperature impact and metallocene and the activator of solid support material react the quantity of obtainable solid support material upper surface reactive group: drying temperature is higher, then site quantity is fewer.Such as, when solid support material is silicon oxide wherein, use it in the first catalyst system synthesis step before, by using nitrogen gas stream oxide/silica, and about 16 hours are heated at about 600 DEG C, thus make it dehydration, typically realize the concentration of surface hydroxyl groups of about 0.7 mmole/gram (mmol/g).Therefore, the definite mol ratio of the surface reaction group on activator and carrier can change.Preferably, this is determined by case, to guarantee that only so many activator joins in solution, because activator will deposit on a support material, and does not leave excessive activator in solution.

Can according to any usual manner, such as, by adding activator in the slurry of carrier in solvent, stir this slurry, such as, until by any technology known in the art, pass through simultaneously ¹hNMR, detects activator with the solution form in solvent, thus mensuration does not leave excessive activator in solution, will deposition activation dosage on a support material.Such as, for the silica support material of heating at about 600 DEG C, the activation dosage joined in slurry makes the mol ratio of hydroxyl (OH) on B and silicon oxide for about 0.5:1 to about 4:1, preferably about 0.8:1 to about 3:1, more preferably from about 0.9:1 is to about 2:1, and most preferably from about 1:1.J.W.Olesik can be used, " InductivelyCoupledPlasma-OpticalEmissionSpectroscopy, " at EncyclopediaofMaterialsCharacterization, C.R.Brundle, C.A.Evans, Jr. edit with S.Wilson, Butterworth-Heinemann, Boston, Mass., 1992, the ICPES (inductively coupled plasma sends out scattering spectrometry) described in 633-644 page, be determined at the boron amount on silicon oxide.In another embodiment, also can add the activator of this consumption, described consumption exceedes the amount at deposited on supports, then such as removes by filtering and wash any excessive activator.

Following paragraph provides all respects of the present invention.

1. a composition, it comprises the many block polyolefin represented with following formula:

PO-(-C=C-Z-) _n-C=C-PO* (I) or

PO-(-C-C-Z-) _n-C-C-PO*(Ia)

Wherein Z is a part for the cyclic monomer with at least one internal double bond, and this part retains after ring-opening metathesis reaction, and preferred Z is C ₁-C ₁₈alkyl or substituted hydrocarbon radical (comprising alkene and substituted olefine), preferred C ₁-C ₁₂alkyl or substituted hydrocarbon radical, preferred C ₁-C ₁₀(substituting group preferably on substituted hydrocarbon radical is C for alkyl or substituted hydrocarbon radical ₁-C ₅alkyl or C ₁-C ₅substituted hydrocarbon radical) (preferable methyl, ethyl, propyl group, butyl, amyl group or its isomer), halogen (such as, Br, Cl, I or F), (aryl ethers or aryl ester, wherein alkyl is C for such as alkyl oxide, alkyl ester for ether or ester ₁-C ₂₀alkyl and aryl are C ₆-C ₂₀aryl, preferable methyl ether, ethyl ether, methyl ethyl ether, butyl ether, propyl ether and similar group), ketone, nitric ether or hydroxyl;

N is 1-about 10,000, especially about 10-about 7500, more specifically about 50-about 5000, and in an aspect, about 100-about 2000.

2. the composition of paragraph 1, at least one wherein in PO and PO* is C ₂₀-C _10,000.

3. the composition of paragraph 1 or 2, wherein many block polyolefin have interior degree of unsaturation, and this passes through ¹³cNMR, shows at the peak at about 128 to about 132ppm places.

4. any one composition of paragraph 1-3, wherein PO* is PO, or PO is PO*.

5. any one composition of paragraph 1-4, wherein many block polyolefin are following mixtures:

PO-(-C=C-Z-) _n-C=C-PO* (I) or

PO-(-C=C-Z-) _n-C=C-PO(II)

PO*-(-C=C-Z-) _n-C=C-PO*(III)

Wherein PO, PO*, n and Z as in paragraph 1 define, preferred I, the mixture of II and III comprises many block polyolefin (I) of about 30%-about 70%, and about 1%-is block polyolefin more than 30% (II) about, and about 1%-about block polyolefin more than 30% (III).

6. any one composition of paragraph 1-4, wherein many block polyolefin are following mixtures:

PO-(-C-C-Z-) _n-C-C-PO*(Ia)

PO-(-C-C-Z-) _n-C-C-PO(IIa)

PO*-(-C-C-Z-) _n-C-C-PO*(IIIa)

Wherein PO, PO*, n and Z as in paragraph 1 define, preferred Ia, the mixture of IIa and IIIa comprises many block polyolefin (Ia) of about 30%-about 70%, and about 1%-is block polyolefin more than 30% (IIa) about, and about 1%-about block polyolefin more than 30% (IIIa).

7. any one composition of paragraph 1-6, wherein the Mn of the many block polyolefin of many block polyolefin is 200-200,000g/mol, preferred 400-20,000g/mol, preferred 300-1500g/mol.

8. any one composition of paragraph 1-7, wherein PO is polypropylene and Mn is about 300-about 20,000g/mol, and preferred PO* is also polypropylene and Mn is about 300-about 20,000g/mol.

9. any one composition of paragraph 1-7, the wherein ethylene/propene copolymer of PO to be Mn be about 300-about 20,000g/mol, the ethylene/propene copolymer of PO* to be also Mn be about 300-about 20,000g/mol.

10. any one composition of paragraph 1-7, wherein PO is polypropylene and Mn is 200-200,000g/mol, preferred 400-20,000g/mol, preferred 300-1500g/mol, preferably about 300-about 20,000g/mol, and PO* is also Mn is 200-200,000g/mol, preferred 400-20,000g/mol, preferred 300-1500g/mol, the preferably ethylene/propene copolymer of about 300-about 20,000g/mol.

Any one composition of 11. paragraph 1-10, at least one the substituted or unsubstituted alkyl wherein in PO and PO* is containing 2-about 18 carbon atoms of having an appointment.

Any one composition of 12. paragraph 1-11, wherein the Mn of many block polyolefin is about 300-about 40,000g/mol.

Any one composition of 13. paragraph 1-17, wherein PO and PO* comprises about 15wt%-and is about 95wt% ethene, and preferably about 30wt%-is about 95wt% ethene.

Any one composition of 14. paragraph 1-13, wherein many block polyolefin are liquid at 25 DEG C.

Any one composition of 15. paragraph 1-13, wherein the viscosity of many block polyolefin at 60 DEG C is greater than 1000cP, is greater than 12,000cP, or is greater than 100,000cP, and be less than 200,000cP, is less than 150,000cP or is less than 100,000cP.

Any one the preparation method of many block polyolefin of 16. paragraph 1-15, the method comprises the steps: olefin metathesis catalyst is contacted with the cyclic hydrocarbon group monomer containing at least one internal double bond with the dimer represented with chemical formula PO-C=C-PO*, wherein PO and PO* is polyolefine, preferred PO and PO* is independently of one another for having 9-10, 000 carbon atom (preferred 20-7500 carbon atom, preferred 30-4000, preferred 40-2000) substituted or unsubstituted alkyl, at least one in preferred PO and PO* has 20-10, 000 carbon atom, preferred 30-2000, C with preferred this cyclic hydrocarbon group monomer ₃-C ₂₀alkyl or substituted hydrocarbon radical, preferred C ₃-C ₁₄alkyl or substituted hydrocarbon radical, preferred C ₃-C ₁₂(substituting group preferably on substituted hydrocarbon radical is C for alkyl or substituted hydrocarbon radical ₁-C ₅alkyl or C ₁-C ₅substituted hydrocarbon radical) (such as methyl, ethyl, propyl group, butyl, amyl group or its isomer), halogen (such as, Br, Cl, I or F), or ether (such as, alkyl oxide or aryl ethers, wherein alkyl is C ₁-C ₂₀alkyl and aryl are C ₆-C ₂₀aryl, preferable methyl ether, ethyl ether, methyl ethyl ether, butyl ether, propyl ether and similar group).

The method of 17. paragraphs 16, wherein olefin metathesis catalyst following formula (IA) represents:

Wherein:

M is the 8th race's metal;

X and X ¹be any anion ligand independently; Or X and X ¹in conjunction with formation two anionic group, and can form the monocycle of maximum 30 non-hydrogen atoms or the polycyclic ring system of maximum 30 non-hydrogen atoms;

L and L ¹be two neutral electron donors independently, L and L ¹can in conjunction with the formation monocycle of maximum 30 non-hydrogen atoms or the polycyclic ring system of maximum 30 non-hydrogen atoms;

L and X in conjunction with formation bidentate monoanionic group, and can form the monocycle of maximum 30 non-hydrogen atoms or the polycyclic ring system of maximum 30 non-hydrogen atoms;

R and R ¹be hydrogen or C independently ₁-C ₃₀substituted or unsubstituted alkyl;

The method of 18. paragraphs 17, wherein

M is Ru or Os;

X and X ¹be halogen independently, alkoxyl group or trifluoromethanesulfonic acid root; Or X and X ¹two anionic groups can be formed, and can in conjunction with the formation monocycle of maximum 30 non-hydrogen atoms or the polycyclic ring system of maximum 30 non-hydrogen atoms;

L and L ¹be phosphine or N-heterocycle carbine independently, L and L ¹can in conjunction with the formation monocycle of maximum 30 non-hydrogen atoms or the polycyclic ring system of maximum 30 non-hydrogen atoms;

R and R ¹be hydrogen or C independently ₁-C ₃₀substituted or unsubstituted alkyl or substituted or unsubstituted C ₄-C ₃₀aryl;

The method of 19. paragraphs 16 or 17, wherein olefin metathesis catalyst be following in one or more of: tricyclohexyl phosphine [1, 3-two (2, 4, 6-trimethylphenyl) imidazoles-2-subunit] [3-phenyl-1H-indenes-1-subunit] ruthenous chloride (II), tricyclohexyl phosphine [3-phenyl-1H-indenes-1-subunit] [1, 3-two (2, 4, 6-trimethylphenyl)-4, 5-dihydro-imidazol--2-subunit] ruthenous chloride (II), tricyclohexyl phosphine [1, 3-two (2, 4, 6-trimethylphenyl)-4, 5-dihydro-imidazol--2-subunit] [(thiophenyl) methylene radical] ruthenous chloride (II), two (tricyclohexyl phosphine)-3-phenyl-1H-indenes-1-subunit ruthenous chloride (II), 1, 3-two (2, 4, 6-trimethylphenyl)-4, 5-glyoxalidine-2-subunit [2-(isopropoxy)-5-(N, N-dimethylamino-sulfonyl) phenyl] methylene chloride ruthenium (II), [1, 3-two (2, 4, 6-trimethylphenyl)-2-imidazolidine subunit]-[2-[[(4-aminomethyl phenyl) imino-] methyl]-4-oil of mirbane phenolic group]-[3-phenyl-1H-indenes-1-subunit] ruthenous chloride (II), benzal base-bis-(tricyclohexyl phosphine) dichloro closes ruthenium, benzal base [1, 3-two (2, 4, 6-trimethylphenyl)-2-imidazolidine subunit] dichloro (tricyclohexyl phosphine) ruthenium, dichloro (an isopropoxy benzene methylene) (tricyclohexyl phosphine) ruthenium (II), (l, 3-two-(2, 4, 6-trimethylphenyl-2-imidazolidine subunit) dichloro (an isopropoxy benzene methylene) ruthenium, l, two (2-the aminomethyl phenyl)-2-imidazolidine subunit of 3-] dichloro (2-isopropoxy benzene methylene) ruthenium (II), [l, 3-two (2, 4, 6-trimethylphenyl)-2-imidazolidine subunit] dichloro [3-(2-pyridyl) propylidene base] ruthenium (II), [l, two (2-the aminomethyl phenyl)-2-imidazolidine subunit of 3-] dichloro (phenylmethylene) (tricyclohexyl phosphine) ruthenium (II), [1, 3-two (2, 4, 6-trimethylphenyl)-2-imidazolidine subunit] dichloro (3-methyl-2-butene fork base) (tricyclohexyl phosphine) ruthenium (II), [l, 3-two (2, 4, 6-trimethylphenyl)-2-imidazolidine subunit] dichloro (benzal base) two (3-bromopyridine) ruthenium (II).

Any one method of 20. paragraph 16-19, the cyclic hydrocarbon group monomer wherein containing at least one internal double bond comprises one or more of cyclopropylene, cyclobutene, cyclopentenes, tetrahydrobenzene, tetrahydrotoluene, suberene, cyclooctadiene, cyclooctene, norbornadiene, norbornylene, cyclobutadiene, cyclohexadiene, cycloheptadiene, cyclooctatetraene, 1,5-cyclooctadiene, 1,5-dimethyl-1,5-cyclooctadiene, Dicyclopentadiene (DCPD), and isomer.

Embodiment

Test and material

As described below, pass through ¹hNMR and DSC characterizes product:

¹HNMR

Or room temperature under or 120 DEG C at, in 5mm probe, use has ¹h frequency is the Varian spectrometer of at least 400MHz, collects ¹hNMR data (for the object of claim, 120 DEG C should be used).Use the maximum pulse of 45 °, the signal of 8 seconds and average 120 transitions between each pulse, record data.Make spectral signal integration, and by be multiplied by with different groups 1000 and by acquired results divided by total carbon number, calculate relative to 1000 carbon, the quantity of degree of unsaturation type.

¹³CNMR

Or room temperature under or 120 DEG C at, in 10mm probe, use has ¹h frequency is the Varian spectrometer of at least 400MHz, collects ¹³cNMR data.During whole acquisition time section, use 90 degree of pulses, for obtaining the digital resolution of 0.1 to 0.12Hz and the acquisition time regulated, the pulse collection time of lag of at least 10 seconds and use frequency sweep square-wave frequency modulation, when there is no gating (gating), the decoupling of continuous print broad band proton.Duration of service, mean value, obtained spectrogram, to provide the signal measuring interested signal fully to the level of noise.Before being inserted in spectrometer magnet, sample is dissolved in tetrachloroethane-d with the concentration of 10wt%-15wt% ₂in.Before data analysis, by setting (-CH ₂-) _nthe chemical potential in-migration of signal is with reference to this spectrogram, wherein n>6 to 29.9ppm.? ¹³in CNMR spectrum, for interior degree of unsaturation site, be used in the signal that about 128-is about 132ppm place, and for reactive end base peak, be used in the signal at about 114 and 137ppm place, the interior location of qualification degree of unsaturation is for quantification.

Pass through ¹³cNMR spectrum, measure polyacrylic microstructure, comprising isotaxy and syndiotaxy diad ([m] and [r]), the concentration of triad ([mm] and [rr]) and five unit groups ([mmmm] and [rrrr]).Symbol " m " or " r " describe the stereochemistry of multipair continuous print propenyl, and wherein " m " refers to meso, and " r " refers to racemize.By sample dissolution at d ₂-l, l, in 2,2-tetrachloroethane, and use 100MHz (or higher) NMR spectrometer, recording light spectrogram at 125 DEG C.The resonance peak of polymkeric substance relates to mmmm=21.8ppm.F.A.Bovey in POLYMERCONFORMATIONANDCONFIGURATION (AcademicPress, New York 1969) and J.Randall at POLYMERSEQUENCEDETERMINATION, ¹³the calculating involved in by NMR characterize polymers is disclosed in CNMRMETHOD (AcademicPress, New York, 1977).

" propylene Tacticity Index ", use [m/r] to express herein, it is according to H.N.Cheng, Macromolecules, and in the 17,1950th page (1984), definition calculates.When [m/r] is 0 to when being less than 1.0, this polymkeric substance is described to syndiotaxy usually, and when [m/r] is 1.0, this polymkeric substance is atactic, and when [m/r] is greater than 1.0, this polymkeric substance is described to isotaxy usually.

GPC

In order to be measured the relevant value of various molecular weight by GPC, use usually at United States Patent(USP) Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; With 6,294, automatization " RapidGPC " system described in 388, carries out Temperature Size Exclusion chromatography, wherein for u. s. mesh, each section at this by reference to introducing fully.This device has a series of 3 30cmx7.5mm Linear column, wherein separately containing PLgel10um, MixB.Use range is the polystyrene standards of 580-3,390,000g/mol, corrects GPC system.Under the oven temperature of the eluent flow velocity of 2.0mL/min and 165 DEG C, operate this system.1,2,4-trichlorobenzene is used as eluent.Polymer samples is dissolved in 1,2,4-trichlorobenzene with the concentration of 0.1-0.9mg/mL.250uL polymers soln is expelled in this system.Use evaporative light scattering detection instrument, the concentration of monitoring eluent interpolymer.Listed molecular weight is relative to linear polystyrene standard substance.

DSC

TA-Q100 instrument carries out dsc (DSC) measure, to determine the fusing point of polymkeric substance.Preannealing sample 15 minutes at 220 DEG C, then makes it cool to room temperature and spends the night.Then, under the speed of 100 DEG C/min, heat this sample to 220 DEG C, then cool under the speed of 50 DEG C/min.During heating collect fusing point.By quick FT-IR spectrography, on BrukerEquinox55+IR, measure the ratio (wt%) being incorporated into the 1-octene in polymkeric substance and ethene in this reflection mode.By vapor deposition techniques, prepare sample in the form of a film.According to 1378 and 4322cm ^-1the ratio of the peak height at place, obtains 1-octene wt%.Use the one group of ethene/1-octene copolymer with known wt%1-octene content scope, correct this method.

All molecular weight are number-average molecular weights, except as otherwise noted.All molecular weight are reported with g/mol.

Use following abbreviation in an embodiment:

Catalyst Z hanIB is l, 3-two (2, 4, 6-trimethylphenyl)-4, 5-glyoxalidine-2-subunit [2-(isopropoxy)-5-(N, N-dimethylamino-sulfonyl) phenyl] methylene chloride ruthenium (II) (StremChemicals, catalog number (Cat.No.) #44-0082) and catalyst n eolystM2 be tricyclohexyl phosphine [3-phenyl-lH-indenes-1-subunit] [1, 3-two (2, 4, 6-trimethylphenyl)-4, 5-glyoxalidine-2-subunit] ruthenous chloride (II) (StremChemicals, catalog number (Cat.No.) #44-7777), aPP is atactic polypropylene(APP), iPP is isotactic polyprophlene, EP is ethylene-propylene copolymer, TCE is 1, 1, 2, 2-tetrachloroethane, h is hour, min is minute, Mn is integration (this USSN12/143 using on June 20th, 2008 to submit to by comparing aliphatic region and alkene region, the scheme that experimental section in 663 describes measures), pass through ¹the spectrometric number-average molecular weight of HNMR.

1,5-cyclooctadiene (1,5-COD) or l, 5-dimethyl-l, 5-cyclooctadiene (1,5-Me ₂-1,5-COD) purchased from SigmaAldrich.The iPP of ethenyl blocking, the EP of ethenyl blocking, and the aPP of ethenyl blocking is prepared as described in WO2009/155471.

Embodiment

Embodiment 1: produce dimer

In glove box, in the 20mL bottle with stirring rod, be introduced through the polypropylene (1.0g, Mn=255) of ethenyl blocking prepared by the method that describes in WO2009/155471.Add methylene dichloride (3mL), and heat this mixture to 40 DEG C.By spatula, add ZhanIB catalyzer (17mg), and at 40 DEG C, stir gained solution 18 hours.Cool this solution to envrionment temperature, at N ₂flow down concentrated, take out from glove box, and smash to pieces (triturate) with MeOH, until oily solid is colourless.This atactic product of finish-drying in vacuum drying oven.Output is 0.9g.

Embodiment 2: produce dimer

In glove box, in the 20mL bottle with stirring rod, be introduced through the polyethylene (1.0g, Mn=484) of ethenyl blocking prepared by the method that describes in WO2009/155471.Add toluene (6mL), and heat this mixture to 55 DEG C.By spatula, add ZhanIB catalyzer (30mg), and stir gained solution at 55 DEG C, until ¹hNMR shows the resonance completely consumed of vinyl.Cool this solution to envrionment temperature, take out from glove box, and under agitation dropwise add in MeOH.By being filtered through course frit, collect gained white precipitate, and in vacuum drying oven finish-drying.Output is 0.95g.

Embodiment 3: produce dimer

In glove box, in the 50mL round-bottomed flask being furnished with agitator, introduce the polypropylene (3.3g, Mn=3571) of ethenyl blocking, toluene (10mL).ZhanIB catalyzer (12mg) is added with the solution form in methylene dichloride (0.5mL).At room temperature stir gained solution, until ¹hNMR shows the resonance completely consumed of vinyl.From glove box, take out this solution, and under agitation dropwise add in MeOH.By decantation, collect gained white precipitate, and in vacuum drying oven finish-drying.Output is 9.8g.

Embodiment 4: produce dimer

In glove box, in the 250mL round-bottomed flask being furnished with agitator, introduce the polypropylene (7.7g, Mn=11,900, Tm=93 DEG C) of ethenyl blocking.Add toluene (100mL), and heat this mixture to 70 DEG C.By spatula, add ZhanIB catalyzer (2.4mg).Connect reflux exchanger, and at 70 DEG C, stir this solution 18 hours.From glove box, take out this solution, and under agitation dropwise join in MeOH.By being filtered through course frit, collect gained white precipitate, and in vacuum drying oven finish-drying.Output is 7.5g.

Under the polyolefinic dimer of ethenyl blocking exists, ring-opening metathesis polymerization (ROMP) cyclooctadiene (COD)

Embodiment 5

In glove box, in the test tube of outfit stirring rod, introduce 1,5-cyclooctadiene (1,5-COD) or l, 5-dimethyl-l, 5-cyclooctadiene (1,5-Me ₂-1,5-COD).As shown in table 1, add polymkeric substance dimer and the toluene of the ethenyl blocking of the embodiment 1-4 of various consumption.Test tube is transferred on the metal block being heated to 55 DEG C.Start and stir, and add ZhanIB catalyzer (the 0.04M toluene solutions of 25 μ L).Continue heating and stir 18 hours, during this period, finding some solvent losses.Add ethyl vinyl ether (0.1mL), any residual active catalyst of quencher.Vacuum dried sample, then passes through gpc analysis.Result is listed in table 1.

Embodiment 6

In glove box, in the 20mL bottle being furnished with stirring rod, introduce cyclooctadiene (13.5mL), the polypropylene dimer (2.62g) of the ethenyl blocking of embodiment 4, CH ₂cl ₂(100mL).Heat this mixture to 40 DEG C.NeolystM2 (105mg) is dissolved in CH ₂cl ₂(2mL) in, and join in round-bottomed flask.Reflux exchanger is fixed on flask, and stirs this solution 18 hours.Then this solution is transferred in steel Parr reactor.By MeOH (20mL) and Et ₃n (1mL) joins in this solution, and seals this reactor, and with 800psiH ₂pressurization.Heat this solution to 80 DEG C, until pass through ¹hNMR spectrography can't detect the resonance of vinyl.Cooling this suspension to room temperature, and by being filtered through raw glass material, collecting solid, with MeOH washing, and in vacuum drying oven finish-drying.Output is 12.2g.

Use preparative temperature rising elution fraction (Prep-TREF), grading is become two kinds of components.Pass through ¹hNMR spectrography, shows containing both polypropylene and polyethylene lower than the component (34 area %) of wash-out at 30 DEG C.Pass through ¹hNMR spectrography, the second component (66 area %) with the peak elution temperature of 98 DEG C shows to contain only polyethylene.Think that polyethylene is derived from the ROMP of cyclooctadiene.

Embodiment 7

In glove box, in the 20mL bottle being furnished with stirring rod, introduce cyclooctadiene (1.35mL).Add various consumption from the polymkeric substance dimer of the ethenyl blocking of embodiment 3-4 and solvent, and as shown in table 2, heat this mixture.NeolystM2 (11mg) is dissolved in CH ₂cl ₂(0.1mL) in, and join in bottle by transfer pipet.Stir this solution 18 hours.Add ethyl vinyl ether (0.1mL), any residual active catalyst of quencher, and from glove box, take out this bottle., mixture is dropwise joined in the MeOH of stirring, and by filtering, the polymkeric substance of collecting precipitation.

This product of vacuum-drying, and transfer in the round-bottomed flask in glove box.Then in this flask, m-xylene (30mL) is introduced, p-toluene sulfonyl hydrazide (3.5 equivalents, relative to alkene) and triethylamine (3.5 equivalents, relative to alkene).By spatula, add 2,6 di t butyl phenol (about 10mg) in a small amount.Heat this mixture to 150 DEG C, until pass through ¹hNMR spectrography, in the aliquots containig be removed, can't detect the resonance of vinyl.Cool this suspension to envrionment temperature, take out from glove box.And dropwise join in the acetone of stirring.By being filtered through the frit of mesoporous, the polymkeric substance of collecting precipitation, with MeOH washing, and in vacuum drying oven finish-drying.Output has been shown in table 2.

Table 1

* measured by GPC

Table 2

Due to all jurisdictional object that this practice allows, all documents described herein at this by reference to introducing, comprising any priority documents, related application and/or test step, its degree makes them not have and conflicts herein, but, condition be any priority documents of not specifying in the document of the initial application submitted to or submission not at this by reference to introducing.According to aforementioned explanation and specific embodiments, it is evident that, although set forth and describe various forms of the present invention, various modification can be made when not departing from the spirit and scope of the present invention.Therefore, the present invention does not intend to be limited.Equally, for the object of Australian law, term " contains " and is regarded as " comprising " synonym with term.Equally, composition before transitional phrase " contains ", whenever are element or a group element, be appreciated that we also consider in said composition, before one or more element have transitional phrase " substantially by ... composition ", and " by ... composition ", " being selected from ... ", or the same combination of "Yes" or a group element, and vice versa.

Claims

1. the composition containing the many block polyolefin represented with following formula:

PO-(-C=C-Z-) n-C=C-PO* or

PO-(-C-C-Z-)n-C-C-PO*

Wherein Z is a part for the cyclic monomer with at least one internal double bond, and this part retains after ring-opening metathesis reaction; PO and PO* is polyolefine independently of one another, and PO and PO* is identical or different, and wherein PO is polypropylene or ethylene/propene copolymer, and Mn is 300-20,000g/mol; Be 1-10 with n, 000.

2. the composition of claim 1, wherein Z is C ₁-C ₁₈alkyl.

3. the composition of claim 1, wherein many block polyolefin are following mixtures

PO-(-C＝C-Z-)n-C＝C-PO*(I),

PO-(-C=C-Z-) n-C=C-PO (II) and

PO*-(-C＝C-Z-)n-C＝C-PO*(III),

4. the composition of claim 3, wherein many block polyolefin (I), (II) and the mixture of (III) comprise many block polyolefin (I) of 30%-70%, the many block polyolefin of 1%-30% (II), and the many block polyolefin of 1%-30% (III).

5. the composition of claim 3, wherein the Mn of many block polyolefin (I) is 200-200,000g/mol.

6. the composition of claim 3, wherein the Mn of many block polyolefin (I) is 300-20,000g/mol.

7. the composition of claim 1, wherein many block polyolefin are following mixtures:

PO-(-C-C-Z-) _n-C-C-PO*(Ia)

PO-(-C-C-Z-) _n-C-C-PO (IIa), and

PO*-(-C-C-Z-) _n-C-C-PO*(IIIa)

8. the composition of claim 7, wherein many block polyolefin (Ia), (IIa) and the mixture of (IIIa) comprise many block polyolefin (Ia) of 30%-70%, the many block polyolefin of 1%-30% (IIa), and the many block polyolefin of 1%-30% (IIIa).

9. the composition of claim 7, wherein the Mn of many block polyolefin (Ia) is 200-200,000g/mol.

10. the composition of claim 7, wherein the Mn of many block polyolefin (Ia) is 300-20,000g/mol.

The composition of 11. claims 1, wherein the viscosity of many block polyolefin at 60 DEG C is greater than 1000cP and is less than 200,000cP.

The composition of 12. claims 1, wherein the bromine number of many block polyolefin is less than 1.8.

The composition of 13. claims 1, wherein PO and/or PO* is isotactic.

Any one the method for many block polyolefin composition of 14. preparation claim 1-13, the method comprises makes olefin metathesis catalyst contact with the cyclic hydrocarbon group monomer containing at least one internal double bond with the polyolefinic dimer of ethenyl blocking.

The method of 15. claims 14, wherein PO and PO* comprises the ethene of 15wt%-95wt%.