Patent Application
20130274427
The present invention relates to a method of controlling the polymer composition of an ethylene copolymer in a process for preparing ethylene copolymers by copolymerizing ethylene and at least one other olefin in the presence of a polymerization catalyst system comprising at least one late transition metal catalyst component (A) having a tridentate ligand which bears at least two ortho, ortho′-disubstituted aryl radicals, at least one Ziegler catalyst component (B), and at least one activating compound (C), to a process for copolymerizing ethylene and at least one other olefin in the presence of such a polymerization catalyst system, to a method for altering the polymer composition of an ethylene copolymer obtained by copolymerizing ethylene and at least one other olefin in the presence of such a polymerization catalyst system and to a method for transitioning from one ethylene copolymer grade to another.
Polyethylene is the most widely used commercial polymer. It can be prepared by a couple of different processes with a broad range of achievable properties. There is however still the wish to improve the products. One measure to enhance the property balance of polyethylenes is preparing so-called bimodal or multimodal polyethylenes. Bimodal polyethylenes are usually obtained by polymerizing or copolymerizing ethylene and optionally comonomers at two different polymerization conditions, which can either arise from polymerizing in a two stage cascade polymerization process at different polymerization conditions or from using mixed or hybrid catalysts, which have different kinds of active sites on one catalyst particle (F. Alt et al., Macromol. Symp. 2001, 163, 135-143). Such polyethylenes have usually a bimodal or at least broad molecular weight distribution and have often also an optimized comonomer distribution. If using a cascade of more than two stages or a mixed catalyst with more than two different kinds of active sites the obtained polymers are no longer “bimodal”. It is therefore common to utilize for such situations the term “multimodal”, while however the term “multimodal” is often also used in the sense of “more than one mode” and consequently including “bimodal”. In the present description the term “multimodal” is as well utilized with the latter meaning, i.e. including “bimodal”.
The advantages of the approach using a mixed catalyst system for preparing multimodal polyethylenes are that it is sufficient to employ only one polymerization reactor and that the produced polyethylenes have a better homogeneity, and thus improved properties, than those resulting from a cascade process since all catalyst particle of a mixed catalyst system are polymerized at the same polymerization conditions, while in a cascade process different catalyst particles have different residence times at the different polymerization conditions and therefore different polymer compositions. However, on the other hand, in a polymerization process with a mixed catalyst system there are only limited possibilities to control the resulting polymer composition because all active sites of the mixed catalyst system undergo the same variations of the polymerization conditions.
WO 96/09328 describes an ethylene polymerization process with a mixed catalyst system comprising a metallocene catalyst component and a Ziegler catalyst component in which water and/or carbon dioxide are co-fed to the polymerization reactor to control the molecular weight distribution of the obtained polyethylene. Also WO 2007/012406 discloses a method for controlling the relative activity of different active centers of a mixed catalyst system by polymerization in the presence of water and/or carbon dioxide, in which the catalyst system comprises a late transition metal catalyst component and a catalyst component comprising cyclopentadienyl ligands.
Another type of mixed catalyst systems for olefin polymerization is described in WO 2008/125208, which teaches mixed catalyst systems comprising a Ziegler catalyst component and a late transition catalyst component for producing multimodal polyethylenes, which have good mechanical properties and good processability. WO 2009/080359 discloses that such catalyst systems may be selectively controlled by varying the amount of activating compound, thus allowing controlling the molecular weight and the comonomer composition of the obtained polyethylene fractions. However, when utilizing an activating compound for controlling the catalyst system it is only possible to influence the properties of the polymers produced by the Ziegler catalyst component of the mixed catalyst system.
Thus, it was the object of the present invention to overcome the disadvantages of the prior art and find an additional way for controlling the resulting polymer composition of a multimodal ethylene copolymer when preparing it with a mixed catalyst system comprising a Ziegler catalyst component and a late transition catalyst component and so give more variation possibilities and flexibility for adjusting the polymerization process and provide a method for producing different ethylene copolymers with one mixed catalyst system.
We have found that this object is achieved by a method of controlling the polymer composition of an ethylene copolymer in a process for preparing ethylene copolymers by copolymerizing ethylene and at least one other olefin in the presence of a polymerization catalyst system comprising
Furthermore, we have found a process for copolymerizing ethylene and at least one other olefin in the presence of such a polymerization catalyst system comprising utilizing the controlling method, a method for altering the polymer composition of an ethylene copolymer obtained by copolymerizing ethylene and at least one other olefin in the presence of such a polymerization catalyst system by varying the polymerization temperature and a method for transitioning from one ethylene copolymer grade to another by using the method for altering the polymer composition.
The features and advantages of the present invention can be better understood via the following description and the accompanying drawings, where
According to the present invention the ethylene copolymers are obtained by copolymerizing ethylene with at least one other olefin, preferably at least one 1-olefin, i.e. a hydrocarbon having terminal double bonds. Suitable other olefins can be functionalized olefinically unsaturated compounds such as ester or amide derivatives of acrylic or methacrylic acid, for example acrylates, methacrylates, or acrylonitrile. Preference is given to nonpolar olefinic compounds, including aryl-substituted 1-olefins. Particularly preferred 1-olefins are linear or branched C3-C12-1-alkenes, in particular linear C3-C10-1-alkenes such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene or branched C2-C10-1-alkenes such as 4-methyl-1-pentene, conjugated and nonconjugated dienes such as 1,3-butadiene, 1,4-hexadiene or 1,7-octadiene or vinylaromatic compounds such as styrene or substituted styrene. It is also possible to polymerize mixtures of various 1-olefins. Suitable olefins also include ones in which the double bond is part of a cyclic structure which can have one or more ring systems. Examples are cyclopentene, norbornene, tetracyclododecene or methylnorbornene or dienes such as 5-ethylidene-2-norbornene, nor-bornadiene or ethylnorbornadiene. It is also possible to copolymerize ethylene with mixtures of two or more other olefins.
The polymerization catalyst system of the present invention comprises at least one late transition metal catalyst component (A) having a tridentate ligand which bears at least two ortho, ortho′-disubstituted aryl radicals, at least one Ziegler catalyst component (B), and at least one activating compound (C).
Late transition metal catalyst component (A) is a late transition metal compound having a tridentate ligand which bears at least two ortho, ortho′-disubstituted aryl radicals and preferably having a bisiminopyridyl ligand bearing two ortho, ortho′-disubstituted aryl radicals. Preferred late transition metals are those of groups 8 to 10 of the Periodic Table of Elements and in particular selected from the group consisting of iron, nickel, palladium, and cobalt. Particularly preferred are catalyst components based on iron or cobalt. The late transition metal catalyst component (A) of the catalyst system of the present invention is obtained by activating a late transition metal complex of the respective ligand structure with a suitable activating agent.
Preferred late transition metal complexes for obtaining the late transition metal catalyst component (A) of the catalyst system of the present invention are iron or cobalt complexes of general formula (I)
where the substituents and indices have the following meaning.
In general formula (I), the three atoms E1A, E2A and E3A can be identical or different. If one of them is phosphorus, then the other two are preferably each carbon. If one of them is nitrogen, then the other two are each preferably nitrogen or carbon, in particular carbon.
In general formula (I) the respective two radicals R8A to R12A can be the same or different. Prefer-ably both substituents R8A to R12A formula (I) of are the same. Preferably at least one radical of the group consisting of R8A, R9A and R11A is fluorine, chlorine, bromine, iodine, —OR13A or —CF3. Especially preferred late transition metal complexes for obtaining the late transition metal catalyst component (A) of the catalyst system of the present invention are iron complexes of general formula (II)
where the substituents and indices have the following meaning.
In general formula (II), the three atoms E1A, E2A and E3A can be identical or different. If one of them is phosphorus, then the other two are preferably each carbon. If one of them is nitrogen, then the other two are each preferably nitrogen or carbon, in particular carbon.
In general formula (II) the respective two radicals R8A to R12A can be the same or different. Prefer-ably both substituents R8A to R12A formula (II) of are the same. Preferably at least one radical of the group consisting of R8A, R9A and R11A is fluorine, chlorine, bromine, iodine, —OR13A or —CF3.
Preferred iron or cobalt compounds may be found in patent application WO 2005/103100.
Especially preferred catalysts components (A) of general formula (I) are 2,6-bis[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine iron(II) chloride; 2,6-bis[1-(2-chloro-6-methylphenylimino)-ethyl]pyridine iron(II) dichloride, 2,6-bis[1-(2,6-dichlorophenylimino)ethyl]pyridine iron(II) dichloride, 2,6-bis[1-(2,4-dichloro-6-methyl-phenylimino)ethyl]pyridine iron(II) dichloride, 2,6-bis[1-(2,6-difluorophenylimino)ethyl]-pyridine iron(II) dichloride, 2,6-bis[1-(2,6-dibromophenylimino)ethyl]-pyridine iron(II) dichloride, 2,6-bis[1-(2,4,6-trimethylphenylimino)ethyl]pyridine iron(II) chloride, 2,6-bis[1-(2-fluoro-6-methylphenylimino)ethyl]pyridine iron(II) chloride or 2,6-bis[1-(2-fluoro-4,6-dimethylphenylimino)ethyl]pyridine iron(II) chloride or the respective dibromides or tribromides.
The preparation of suitable iron complexes is described, for example, in J. Am. Chem. Soc. 120, p. 4049 ff. (1998), J. Chem. Soc., Chem. Commun. 1998, 849, and WO 98/27124.
Ziegler catalysts components (B) are well known in the art and are described for example in ZIEGLER CATALYSTS 363-386 (G. Fink, R. Mülhaupt and H. H. Brintzinger, eds., Springer-Verlag 1995). For the purposes of the present application, the expression Ziegler catalyst also includes the catalysts referred to as Ziegler-Natta catalysts in the literature.
The Ziegler catalyst component (B) preferably comprises a solid component comprising a compound of titanium or vanadium, a compound of magnesium and optionally but preferably a particulate inorganic oxide as support.
As titanium compounds, use is generally made of the halides or alkoxides of trivalent or tetrava-lent titanium, with titanium alkoxy halogen compounds or mixtures of various titanium compounds also being possible. Examples of suitable titanium compounds are TiBr3, TiBr4, TiCl3, TiCl4, Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(O-i-C3H7)Cl3, Ti(O-n-C4H9)Cl3, Ti(OC2H5)Br3, Ti(O-n-C4H9)Br3, Ti(OCH3)2Cl2, Ti(OC2H5)2Cl2, Ti(O-n-C4H9)2Cl2, Ti(OC2H5)2Br2, Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(O-n-C4H9)3Cl, Ti(OC2H5)3Br, Ti(OCH3)4, Ti(OC2H5)4 or Ti(O-n-C4H9)4. Preference is given to using titanium compounds which comprise chlorine as the halogen. Preference is likewise given to titanium halides which comprise only halogen in addition to titanium and among these especially titanium chlorides and in particular titanium tetrachloride. Among the vanadium compounds, particular mention may be made of the vanadium halides, the vanadium oxyhalides, the vanadium alkoxides and the vanadium acetylacetonates. Preference is given to vanadium compounds in the oxidation states 3 to 5.
In the production of the solid component, at least one compound of magnesium is preferably additionally used. Suitable compounds of this type are halogen-comprising magnesium compounds such as magnesium halides, and in particular chlorides or bromides and magnesium compounds from which the magnesium halides can be obtained in a customary way, e.g. by reaction with halogenating agents. For the present purposes, halogens are chlorine, bromine, iodine or fluorine or mixtures of two or more halogens, with preference being given to chlorine or bromine, and in particular chlorine.
Possible halogen-comprising magnesium compounds are in particular magnesium chlorides or magnesium bromides. Magnesium compounds from which the halides can be obtained are, for example, magnesium alkyls, magnesium aryls, magnesium alkoxy compounds or magnesium aryloxy compounds or Grignard compounds. Suitable halogenating agents are, for example, halogens, hydrogen halides, SiCl4 or CCl4 and preferably chlorine or hydrogen chloride.
Examples of suitable halogen-free compounds of magnesium are diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, di-n-butylmagnesium, di-sec-butylmagnesium, di-tert-butylmagnesium, diamylmagnesium, n-butylethylmagnesium, n-butyl-sec-butylmagnesium, n-butyloctylmagnesium, diphenylmagnesium, diethoxymagnesium, di-n-propyloxymagnesium, diisopropyloxymagnesium, di-n-butyloxymagnesium, di-sec-butyloxymagnesium, di-tert-butyloxymagnesium, diamyloxymagnesium, n-butyloxyethoxymagnesium, n-butyloxy-sec-butyloxymagnesium, n-butyloxyoctyloxymagnesium and diphenoxymagnesium. Among these, preference is given to using n-butylethylmagnesium or n-butyloctylmagnesium.
Examples of Grignard compounds are methylmagnesium chloride, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, n-propylmagnesium chloride, n-propyl-magnesium bromide, n-butylmagnesium chloride, n-butylmagnesium bromide, sec-butyl-magnesium chloride, sec-butylmagnesium bromide, tert-butylmagnesium chloride, tert-butyl-magnesium bromide, hexylmagnesium chloride, octylmagnesium chloride, amylmagnesium chloride, isoamylmagnesium chloride, phenylmagnesium chloride and phenylmagnesium bromide.
As magnesium compounds for producing the particulate solids, preference is given to using, apart from magnesium dichloride or magnesium dibromide, the di(C1-C10-alkyl)magnesium compounds.
It is also possible to use commercially available Ziegler catalysts as Ziegler catalysts components (B) of the polymerization catalyst system of the present invention.
Activating compounds (C) are compounds which are able to react with late transition metal catalyst component (A) and with the Ziegler catalyst component (B) to convert them into catalytically active compounds. Preferred activating compounds (C) are Lewis acids
In a preferred embodiment of the present invention activating compounds (C) are strong Lewis acid compounds of the general formula (III)
MCR1CR2CR3C
wherein
Further examples of strong Lewis acids are mentioned in WO 00/31090.
Suitable activating compounds (C) comprising aluminum are trialkylaluminum and compounds derived therefrom, in which an alkyl group has been replaced by an alkoxy group or by a halogen atom, for example by chlorine or bromine. The alkyl groups can be identical or different. Both linear and branched alkyl groups are possible.
Preference is given to trialkylaluminum compounds wherein the alkyl groups have from 1 to 8 carbon atoms, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylalumi-num, methyldiethylaluminum and mixtures thereof. According to a preferred embodiment, the activating compound (C) is selected from the group consisting of trimethylaluminum (TMA), trieth-ylaluminum (TEA), triisobutylaluminum (TIBA) and mixtures thereof.
Suitable activating compounds (C) also include boranes and boroxins, e.g. trialkylborane, triaryl-borane or trimethylboroxin. Particular preference is given to boranes bearing at least two perfluorinated aryl radicals. Particular preference is given to compounds of formula (III) wherein R1C, R2C and R3C are identical, such as triphenylborane, tris(4-fluorophenyl)borane, tris-(3,5-difluorophenyl)borane, tris(4-fluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(tolyl)borane, tris(3,5-dimethylphenyl)borane, tris(3,5-difluorophenyl)borane or tris-(3,4,5 trifluorophenyl)borane.
Tris(pentafluorophenyl)borane is preferably used.
Such activating compounds (C) may be prepared by reaction of aluminum or boron compounds of the formula (III) with water, alcohols, phenol derivatives, thiophenol derivatives or aniline derivatives, with the halogenated and especially the perfluorinated alcohols and phenols being of particular importance. Examples of particularly suitable compounds are pentafluorophenol, 1,1-bis(pentafluorophenyl)methanol and 4-hydroxy-2,2′,3,3′,4,4′,5,5′,6,6′-nonafluorobiphenyl. Examples of combinations of compounds of the formula (III) with Brönsted acids are first and fore-most trimethylaluminum/pentafluorophenol, trimethylaluminum/1-bis(pentafluorophenyl) methanol, trimethylaluminum/4-hydroxy-2,2′,3,3′,4,4′,5,5′,6,6′-nonafluorobiphenyl, triethylaluminum/pentafluorophenol, triisobutylaluminum/pentafluorophenol and triethylaluminum/4,4′-dihydroxy-2,2′,3,3′,5,5′,6,6′-octafluorobiphenyl hydrate.
In further suitable aluminum and boron compounds of the formula (III), R1C is an OH group, as in, for example, boronic acids and borinic acids, with preference being given to borinic acids having perfluorinated aryl radicals, for example (C6F5)2BOH.
Strong Lewis acids which are suitable as activating compounds (C) also include the reaction products of a boric acid with two equivalents of an aluminum trialkyl or the reaction products of an aluminum trialkyl with two equivalents of an acidic fluorinated, preferably perfluorinated hydrocar-bon compounds, such as pentafluorophenol or bis(pentafluorophenyl)borinic acid.
Further preferred activating compounds (C), which can be used together with Lewis acid compounds of the general formula (III) or in place of them are, are one or more aluminoxanes. As aluminoxanes, it is possible to use, for example, the compounds described in WO 00/31090. Particularly suitable aluminoxanes are open-chain or cyclic aluminoxane compounds of the general formula (III) or (IV)
where
A particularly suitable aluminoxane compound is methylaluminoxane.
These oligomeric aluminoxane compounds are usually prepared by controlled reaction of a solution of trialkylaluminum, preferably trimethylaluminum, with water. In general, the oligomeric aluminoxane compounds obtained in this way are present as mixtures of both linear and cyclic chain molecules of various lengths, so that l is to be regarded as an average. The aluminoxane compounds can also be present in admixture with other metal alkyls, usually with aluminum alkyls.
Furthermore, modified aluminoxanes in which some of the hydrocarbon radicals have been re-placed by hydrogen atoms or alkoxy, aryloxy, siloxy or amide radicals can also be used in place of the aluminoxane compounds of the general formula (III) or (IV).
The molar ratio of the metal (preferably Al) in activating compound (C) to the late transition metal (preferably Fe) of catalyst (A) usually ranges from 20,000:1 to 1:1, preferably from 1,000:1 to 1:1, and even more preferably from 500:1 to 1:1.
The molar ratio of the metal of the Ziegler catalyst component (B) to the late transition metal of catalyst component (A) to is preferably in the range from 500:1 to 1:100, more preferably from 100:1 to 1:50, and even more preferably from 50:1 to 1:1.
Both the late transition metal complex component (A) and the Ziegler catalyst component (B) and also the activating compounds (C) are preferably used in a solvent, with preference being given to aromatic hydrocarbons having from 6 to 20 carbon atoms, in particular xylenes, toluene, pentane, hexane, heptane or mixtures of these.
The catalyst components (A), (B), and (C) can be used either alone or together with further components as catalyst system for olefin polymerization. Further optional components may be one or more organic or inorganic supports (D). It is possible to feed all catalyst components (A), (B), and (C) independently to the polymerization reaction, where one or more of the components (A), (B), and (C) can also be combined with further optional components like a support or solvent. It is possible to combine first all components (A), (B), and (C), and optional further components, and feed this mixture to the polymerization reaction or to combine one or both of components (A) and (B) with activating compounds (C) and feed the resulting mixtures to the polymerization reaction. It is further possible to first combined late transition metal catalyst compound (A) and Ziegler catalyst component (B), optionally on a support or in a solvent, and feed this mixture separately from the activating compounds (C) to the polymerization reaction.
In particular, to enable the late transition metal catalyst compound (A) and the Ziegler catalyst component (B) to be used in the gas phase or in suspension in polymerization processes, it is often advantageous for the complexes to be used in the form of a solid, i.e. for them to be applied to a solid support (D). Furthermore, the supported complexes have a high productivity. The late transition metal catalyst (A) and/or the Ziegler catalysts (B) can therefore optionally be immobilized on an organic or inorganic support (D) and be used in supported form in the polymerization. This enables, for example, deposits in the reactor to be avoided and the polymer morphology to be controlled.
As support materials, preference is given to using silica gel, magnesium chloride, aluminum oxide, mesoporous materials, aluminosilicates, hydrotalcites and organic polymers such as polyethylene, polypropylene, polystyrene, polytetrafluoroethylene or polymers having polar functional groups, for example copolymers of ethene and acrylic esters, acrolein or vinyl acetate.
A preferred catalyst composition to be used in the process of the invention comprises one or more support components. It is possible for both the late transition metal catalyst (A) and the Ziegler catalyst (B) to be supported, or only one of the two components can be supported. In a preferred variant, both components (A) and (B) are supported. The two components (A) and (B) can have been applied to different supports or together to a joint support. The components (A) and (B) are preferably applied to a joint support in order to ensure relative spatial proximity of the various catalyst sites and thus achieve good mixing of the different polymers formed.
To produce the catalyst systems of the invention, one of the components (A) and one of the components (B) and/or activator (C) are preferably immobilized on the support (D) by physisorption or by means of a chemical reaction, i.e. covalent bonding of the components, with reactive groups of the support surface.
The order in which support component (D), late transition metal complex (A), Ziegler catalyst (B) and the activating compound (C) are combined is in principle immaterial. After the individual process steps, the various intermediates can be washed with suitable inert solvents, e.g. aliphatic or aromatic hydrocarbons.
The late transition metal complex (A), the Ziegler catalyst (B) and the activating compound (C) can be immobilized independently of one another, e.g. in succession or simultaneously. Thus, the support component (D) can firstly be brought into contact with the activating compound or compounds (C) or the support component (D) can firstly be brought into contact with the Ziegler catalyst (B) and/or the late transition metal complex (A). Preactivation of the Ziegler catalyst (B) with one or more activating compounds (C) before mixing with the support (D) is also possible. The late transition metal component can, for example, be reacted simultaneously with the transition metal complex with the activating compound (C) or can be preactivated separately by means of this. The preactivated late transition metal complex (A) can be applied to the support before or after the preactivated Ziegler catalyst (B). In one possible embodiment, the late transition metal complex (A) and/or the Ziegler catalyst (B) can also be prepared in the presence of the support material. A further method of immobilization is prepolymerization of the catalyst system with or without prior application to a support.
The immobilization is generally carried out in an inert solvent which can be filtered off or evaporated after the immobilization. After the individual process steps, the solid can be washed with suitable inert solvents, e.g. aliphatic or aromatic hydrocarbons, and dried. The use of the still moist, supported catalyst is also possible.
In a preferred form of the preparation of the supported catalyst system, at least one late transition metal complex (A) is brought into contact with an activating compound (C) and subsequently mixed with the dehydrated or passivated support material (D). The Ziegler catalyst (B) is likewise brought into contact with at least one activating compound (C) in a suitable solvent, preferably giving a soluble reaction product, an adduct or a mixture. The preparation obtained in this way is then mixed with the immobilized late transition metal complex, which is used either directly or after separating off the solvent, and the solvent is completely or partly removed. The resulting supported catalyst system is preferably dried to ensure that the solvent is removed completely or largely from the pores of the support material. The supported catalyst is preferably obtained as a free-flowing powder. Examples of the industrial implementation of the above process are described in WO 96/00243, WO 98/40419 or WO 00/05277. A further preferred embodiment comprises firstly applying the activating compound (C) to the support component (D) and subsequently bringing this supported compound into contact with the late transition metal complex (A) and the Ziegler catalyst (B).
As support component (D), preference is given to using finely divided supports which can be any organic or inorganic solid. In particular, the support component (D) can be a porous support such as talc, a sheet silicate such as montmorillonite or mica, an inorganic oxide or a finely divided polymer powder (e.g. polyolefin or polymer having polar functional groups).
The support materials used preferably have a specific surface area in the range from 10 to 1000 m2/g, a pore volume in the range from 0.1 to 5 ml/g and a mean particle size of from 1 to 500 μm. Preference is given to supports having a specific surface area in the range from 50 to 700 m2/g, a pore volume in the range from 0.4 to 3.5 ml/g and a mean particle size in the range from 5 to 350 μm. Particular preference is given to supports having a specific surface area in the range from 200 to 550 m2/g, a pore volume in the range from 0.5 to 3.0 ml/g and a mean particle size of from 10 to 150 μm.
The inorganic support can be subjected to a thermal treatment, e.g. to remove adsorbed water. Such a drying treatment is generally carried out at temperatures in the range from 50 to 1000° C., preferably from 100 to 600° C., with drying at from 100 to 200° C. preferably being carried out under reduced pressure and/or under a blanket of inert gas (e.g. nitrogen), or the inorganic support can be calcined at temperatures of from 200 to 1000° C. to obtain, if appropriate, the desired structure of the solid and/or the desired OH concentration on the surface. The support can also be treated chemically using customary dessicants such as metal alkyls, preferably aluminum alkyls, chlorosilanes or SiCl4 or else methylaluminoxane. Appropriate treatment methods are described, for example, in WO 00/31090.
Organic support materials such as finely divided polyolefin powders (e.g. polyethylene, polypropylene or polystyrene) can also be used and should preferably likewise be freed of adhering moisture, solvent residues or other impurities by means of appropriate purification and drying operations before use. It is also possible to use functionalized polymer supports, e.g. ones based on polystyrene, polyethylene, polypropylene or polybutylene, via whose functional groups, for example ammonium or hydroxyl groups, at least one of the catalyst components can be immobilized. Polymer blends can also be used.
Inorganic oxides suitable as support component (D) may be found in groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic Table of the Elements. Examples of oxides preferred as supports comprise silicon dioxide, aluminum oxide and mixed oxides of the elements calcium, aluminum, silicon, magnesium or titanium and also corresponding oxide mixtures. Other inorganic oxides which can be used either alone or in combination with the abovementioned preferred oxidic supports are, for example, MgO, CaO, AIPO4, ZrO2, TiO2, B2O3 or mixtures thereof.
Further preferred inorganic support materials are inorganic halides such as MgCl2 or carbonates such as Na2CO3, K2CO3, CaCO3, MgCO3, sulfates such as Na2SO4, Al2(SO4)3, BaSO4, nitrates such as KNO3, Mg(NO3)2 or Al(NO3)3.
Preference is given to using silica gels as solid support materials (D) for catalysts for olefin polymerization since this material makes it possible to produce particles whose size and structure make them suitable as supports for olefin polymerization. Spray-dried silica gels, which are spherical agglomerates of smaller granular particles, viz. the primary particles, have been found to be particularly useful here. The silica gels can be dried and/or calcined before use.
The silica gels used are generally used as finely divided powders having a mean particle diameter D50 of from 5 to 200 μm, preferably from 10 to 150 μm, particularly preferably from 15 to 100 μm and more preferably from 20 to 70 μm, and usually have pore volumes of from 0.1 to 10 cm3/g, preferably from 0.2 to 5 cm3/g, and specific surface areas of from 30 to 1000 m2/g, preferably from 50 to 800 m2/g and preferably from 100 to 600 m2/g. The Ziegler catalyst (A) is preferably applied in such an amount that the concentration of the transition metal from the Ziegler catalyst (A) in the finished catalyst system is from 1 to 100 μmol, preferably from 5 to 80 μmol and particularly preferably from 10 to 60 μmol, per g of support (D).
The late transition metal catalyst (A) is preferably applied in such an amount that the concentration of the late transition metal from the late transition metal catalyst (A) in the finished catalyst system is from 1 to 200 μmol, preferably from 5 to 100 μmol and particularly preferably from 10 to 70 μmol, per g of support (D). The Ziegler catalyst (B) is preferably applied in such an amount that the concentration of transition metal from the Ziegler catalyst (B) in the finished catalyst system is from 1 to 200 μmol, preferably from 5 to 100 μmol and particularly preferably from 10 to 70 μmol, per g of support (D).
It is also possible for the catalyst system firstly to be prepolymerized with 1-olefins, preferably linear C2-C10-1-alkenes and more preferably ethylene or propylene, and the resulting prepolymer-ized catalyst solid then to be used in the actual polymerization. The weight ratio of catalyst solid used in the prepolymerization to a monomer polymerized onto it is preferably in the range from 1:0.1 to 1:1000, preferably from 1:1 to 1:200. Furthermore, a small amount of an olefin, preferably an 1-olefin, for example vinylcyclohexane, styrene or phenyldimethylvinylsilane, as modifying component, an antistatic or a suitable inert compound such as a wax or oil can be added as additive during or after the preparation of the catalyst system. The molar ratio of additives to the sum of late transition metal catalyst (A) and Ziegler catalyst (B) is usually from 1:1000 to 1000:1, preferably from 1:5 to 20:1.
The process can be carried out using all industrially known low-pressure polymerization methods at temperatures in the range from −20 to 200° C., preferably from 25 to 150° C. and particularly preferably from 40 to 130° C., and under pressures of from 0.1 to 20 MPa and particularly preferably from 0.3 to 5 MPa. The polymerization can be carried out batchwise or preferably continuously in one or more stages. Solution processes, suspension processes, stirred gas-phase processes and gas-phase fluidized-bed processes are all possible. Processes of this type are generally known to those skilled in the art. Among the polymerization processes mentioned, gas-phase polymerization, in particular in gas-phase fluidized-bed reactors and suspension polymerization, in particular in loop reactors or stirred tank reactors, are preferred.
In a preferred embodiment of the present invention the polymerization process is a suspension polymerization in a suspension medium, preferably in an inert hydrocarbon such as isobutane or mixtures of hydrocarbons or else in the monomers themselves. Suspension polymerization temperatures are usually in the range from −20 to 115° C., preferably from 50 to 110° C. and particularly preferably from 60 to 100° C., and the pressure is in the range of from 0.1 to 10 MPa and preferably from 0.3 to 5 MPa. The solids content of the suspension is generally in the range of from 10 to 80 wt.-%. The polymerization can be carried out both batchwise, e.g. in stirred autoclaves, and continuously, e.g. in tubular reactors, preferably in loop reactors. In particular, it can be carried out by the Phillips PF process as described in U.S. Pat. No. 3,242,150 and U.S. Pat. No. 3,248,179.
Suitable suspension media are all media which are generally known for use in suspension reactors. The suspension medium should be inert and be liquid or supercritical under the reaction conditions and should have a boiling point which is significantly different from those of the monomers and comonomers used in order to make it possible for these starting materials to be recovered from the product mixture by distillation. Customary suspension media are saturated hydrocarbons having from 4 to 12 carbon atoms, for example isobutane, butane, propane, isopentane, pentane and hexane, or a mixture of these, which is also known as diesel oil.
In a preferred suspension polymerization process, the polymerization takes place in a cascade of two or preferably three or four stirred vessels. The molecular weight of the polymer fraction prepared in each of the reactors is preferably set by addition of hydrogen to the reaction mixture. The polymerization process is preferably carried out with the highest hydrogen concentration and the lowest comonomer concentration, based on the amount of monomer, being set in the first reactor. In the subsequent further reactors, the hydrogen concentration is gradually reduced and the comonomer concentration is altered, in each case once again based on the amount of monomer. A further, preferred suspension polymerization process is suspension polymerization in loop reactors, where the polymerization mixture is pumped continuously through a cyclic reactor tube. As a result of the pumped circulation, continual mixing of the reaction mixture is achieved and the catalyst introduced and the monomers fed in are distributed in the reaction mixture. Furthermore, the pumped circulation prevents sedimentation of the suspended polymer. The removal of the heat of reaction via the reactor wall is also promoted by the pumped circulation. In general, these reactors consist essentially of a cyclic reactor tube having one or more ascending legs and one or more descending legs which are enclosed by cooling jackets for removal of the heat of reaction and also horizontal tube sections which connect the vertical legs. The impeller pump, the catalyst feed facilities and the monomer feed facilities and also the discharge facility, thus normally the settling legs, are usually installed in the lower tube section. However, the reactor can also have more than two vertical tube sections, so that a meandering arrangement is obtained.
The polymer is generally discharged continuously from the loop reactor via settling legs. The settling legs are vertical attachments which branch off from the lower reactor tube section and in which the polymer particles can sediment. After sedimentation of the polymer has occurred to a particular degree, a valve at the lower end of the settling legs is briefly opened and the sedimented polymer is discharged discontinuously.
Preferably, the suspension polymerization is carried out in the loop reactor at an ethylene concentration of at least 5 mole percent, preferably 10 mole percent, based on the suspension medium. In this context, suspension medium does not mean the fed suspension medium such as isobutane alone but rather the mixture of this fed suspension medium with the monomers dissolved therein. The ethylene concentration can easily be determined by gas-chromatographic analysis of the suspension medium.
In a further preferred embodiment of the present invention the polymerization process is carried out in a horizontally or vertically stirred or fluidized gas-phase reactor.
Particular preference is given to gas-phase polymerization in a fluidized-bed reactor, in which the circulated reactor gas is fed in at the lower end of a reactor and is taken off again at its upper end. When such a process is employed for the polymerization of 1-olefins, the circulated reactor gas is usually a mixture of the 1-olefins to be polymerized, inert gases such as nitrogen and/or lower alkanes such as ethane, propane, butane, pentane or hexane and optionally a molecular weight regulator such as hydrogen. The use of nitrogen or propane as inert gas, if appropriate in combination with further lower alkanes, is preferred. The velocity of the reactor gas has to be sufficiently high firstly to fluidize the mixed bed of finely divided polymer present in the tube and serving as polymerization zone and secondly to remove the heat of polymerization effectively. The polymerization can also be carried out in a condensed or super-condensed mode, in which part of the circulating gas is cooled to below the dew point and returned to the reactor separately as a liquid and a gas phase or together as a two-phase mixture in order to make additional use of the enthalpy of vaporization for cooling the reaction gas.
In gas-phase fluidized-bed reactors, it is advisable to work at pressures of from 0.1 to 10 MPa, preferably from 0.5 to 8 MPa and in particular from 1.0 to 3 MPa. In addition, the cooling capacity depends on the temperature at which the polymerization in the fluidized bed is carried out. The process is advantageously carried out at temperatures of from 30 to 160° C., particularly preferably from 65 to 125° C., with temperatures in the upper part of this range being preferred for copolymers of relatively high density and temperatures in the lower part of this range being preferred for copolymers of lower density.
It is also possible to use a multizone reactor in which two polymerization zones are linked to one another and the polymer is passed alternately a plurality of times through these two zones, with the two zones also being able to have different polymerization conditions. Such a reactor is described, for example, in WO 97/04015 and WO 00/02929.
The different or else identical polymerization processes can also, if desired, be connected in series and thus form a polymerization cascade. A parallel arrangement of reactors using two or more different or identical processes is also possible. However, the polymerization is preferably carried out in a single reactor.
The method of the present invention is characterized in that the temperature, at which the polymerization is carried out, is varied. By changing the polymerization temperature it is possible to modify the composition of the obtained ethylene copolymer and the ratio of the portion of the ethylene copolymer, which is obtained from polymerization by late transition metal catalyst component (A), and the portion, which is obtained from polymerization by Ziegler catalyst component (B), is shifted. The variation of the polymerization temperature allows controlling the polymerization process and especially the composition of the obtained ethylene copolymer.
The method of controlling the composition ethylene copolymers according to the present invention can be used accompanied by varying the amount of added activating compound (C). Varying both temperature and the amount of added activating compound allows a more sophisticated approach for adjusting the ratio of the portions of the produced ethylene copolymer prepared by the different catalyst components.
Usually all processes for copolymerizing ethylene and other olefins are carried out in the presence of hydrogen as regulator to control the molecular weight of the obtained ethylene copolymer. According to a preferred embodiment of the present invention also the amount of added hydrogen is varied, preferably to compensate for a shift of the molecular weight of the ethylene copolymer caused by the modification of the polymerization conditions.
Without being tied to this explanation, the ability of effectively controlling the composition of the obtained ethylene copolymer may be due to different effects of the measures temperature variation, variation of the concentration of activating compound (C), and variation of the hydrogen concentration on the polymerization behavior of catalyst components (A) and (B). It has been found that increasing the polymerization temperature and increasing the concentration of activating compound (C) is enhancing the polymerization activity of the Ziegler catalyst component (B). On the other hand, the polymerization activity of the late transition metal catalyst component (A) is decreased by increasing the polymerization temperature while a variation of the concentration of the activating compound (C) has only a negligible influence on the polymerization activity of the late transition metal catalyst component (A). Furthermore, a variation of the hydrogen concentration affects only the molecular weight of the portion of the ethylene copolymer, which is obtained from polymerization by the Ziegler catalyst component (B) while it has no effect on the molecular weight of the portion of the ethylene copolymer, which is obtained from polymerization by late transition metal catalyst component (A).
The controlling method of the present invention guaranties an effective adjustment the composition of the prepared ethylene copolymers. This allows, for example, compensating for differences in the composition of different lots of a catalyst system or for different qualities of educts of the polymerization reaction or for different levels of impurities, which interact differently with the components of the catalyst system. This however also provides the possibility to intentionally altering the composition of an ethylene copolymer and preparing, for example, different grades of ethylene copolymers with one catalyst system. Transitioning from one grade to another can then take place by such altering of the composition of the ethylene.
Accordingly, one embodiment of the present invention refers to a process for copolymerizing ethylene and at least one other olefin in the presence of a polymerization catalyst system as defined above comprising utilizing such a controlling method. Another embodiment refers to a method for altering the composition of an ethylene copolymer obtained by copolymerizing ethylene and at least one other olefin in the presence of a polymerization catalyst system as defined above by varying the polymerization temperature and a further embodiment refers to a method for transitioning from one ethylene copolymer grade to another by utilizing the method for altering the composition of an ethylene copolymer.
The invention is illustrated below with the aid of examples, without being restricted thereto.
If not otherwise indicated, all synthesis and polymerizations were carried out in an argon atmosphere. All suspending agents were washed by argon and dried through molecular sieves before being used.
Density was determined according to DIN EN ISO 1183-1:2004, Method A (Immersion) with compression molded plaques of 2 mm thickness. The compression molded plaques were prepared with a defined thermal history: Pressed at 180° C., 20 MPa for 8 min with subsequent crystallization in boiling water for 30 min.
The vinyl double bond content, i.e. the content of vinyl groups/1000 carbon atoms, was deter-mined by means of IR in accordance with ASTM D 6248 98. The amount of vinyl groups per 1000 carbon atoms is, under the applied polymerization conditions, a measure for the proportion of the polymer, which was polymerized by the late transition metal catalyst component.
The melt flow rate MFR21.6 was determined according to DIN EN ISO 1133:2005, condition G at a temperature of 190° C. under a load of 21.6 kg.
The melt flow rate MFR5 was determined according to DIN EN ISO 1133:2005, condition T at a temperature of 190° C. under a load of 5 kg.
The Flow Rate Ratio FRR is the ratio of MFR21.6/MFR5
The swell ratio SR was measured in a high-pressure capillary rheometer (Rheotester 1000, Göttfert Werkstoff-Prüfmaschinen GmbH, Buchen, Germany) at a shear rate of 1440 1/s in a 30/2/2/20 round-perforation die with conical inlet (angle=20°, D=2 mm, L=2 mm, total length=30 mm) at a temperature of 190° C., using a laser-diode placed at a distance of 78 mm from the die exit. SR is defined as difference dmax−dd divided by dd with dmax being the maximum diameter of the strand and dd being the diameter of the die.
The recording of the GPC (Gel Permeation Chromatography) curves was carried out by high-temperature gel permeation chromatography using a method described in ISO 16014-1:2003(E) and ISO 16014-4:2003(E): solvent 1,2,4-trichlorobenzene (TCB), temperature of apparatus and solutions 135° C. and as concentration detector a PolymerChar (Valencia, Paterna 46980, Spain) IR-4 infrared detector, capable for use with TCB. A WATERS Alliance 2000 equipped with the following precolumn SHODEX UT-G and separation columns SHODEX UT 806 M (3×) and SHODEX UT 807 connected in series was used. The solvent was vacuum distilled under nitrogen and was stabilized with 0.025 wt.-% of 2,6-di-tert-butyl-4-methylphenol. The flow rate used was 1 mL/min, the injection was 400 μL and polymer concentration was in the range of 0.01 wt.-%<conc. <0.05 wt.-%. The molecular weight calibration was established by using mon-odisperse polystyrene (PS) standards from Polymer Laboratories (now Varian Inc., Essex Road, Church Stretton, Shropshire, SY6 6AX, UK) in the range from 580 g/mol up to 11600000 g/mol and additionally Hexadecane. The calibration curve was then adapted to Polyethylene (PE) by means of the Universal Calibration method according to ISO 16014-2:2003(E). The Mark-Houwing parameters used were for PS: kPS=0.000121 dL/g, αPS=0.706 and for PE kPE=0.000406 dL/g, αPE=0.725, valid in TCB at 135° C. Data recording, calibration and calculation was carried out using NTGPC_Control_V6.3.00 and NTGPC_V6.4.05 (hs GmbH, Hauptstraβe 36, D-55437 Ober-Hilbersheim), respectively.
35.0 g 2,6-diacetylpyridine (0.215 mol), 50 g of Sicapent® (phosphorus pentoxide drying agent) obtained from Merck KGaA, Darmstadt, Germany and 76.8 g (0.493 mol) 2-chloro-4,6-dimethyl-aniline were dissolved in 1500 mL of THF. The mixture was heated under reflux conditions for 42 hours. The mixture was subsequently filtered at 22° C. The filter cake was washed with 50 mL of THF. The solvent of the combined filtrates was distilled off. 250 mL of methanol were added and the mixture was stirred for 1 hour. A yellow suspension was formed in this way. The solid product was isolated by filtration, twice washed with 20 mL of methanol and subsequently dried. Yield: 58.0 g (61.7%) of 2,6-bis[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine.
10 g of 2,6-bis[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine (22.81 mmol) were dissolved in 100 mL of THF. 3.86 g of FeCl2*4H2O (19.4 mmol) were added and the mixture was stirred for 4 h at 22° C. A blue precipitate formed. The solid product was isolated by filtration at 22° C., washed with 100 mL of pentane and subsequently dried. Yield: 13.66 g (94%) of 2,6-bis[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine iron(II) dichloride.
A four liter four-necked round-bottomed flask was charged with 220 g silica gel (Sylopol® 2107 obtained from Grace GmbH & Co. KG, Worms, which had previously been calcinated for 6 hours at 600° C.) and 700 mL of heptane. The temperature was raised to 50° C. Thereafter hexamethyl-disilazane (1.5 mmol per gram of silica gel) obtained from Sigma-Aldrich Chemie GmbH, Steinheim, Germany was added dropwise within 3 min at 50° C. and stirred for 30 min. The liquid phase was decanted and the solid was washed with heptane (500 mL) in three portions.
330 ml of a 1 M in heptane solution of dibutylmagnesium (obtained from Sigma-Aldrich Chemie GmbH, Steinheim, Germany) were added at 22° C. within 10 minutes and then the suspension was heated to 50° C. and stirred for 60 minutes. The temperature was reduced to 22° C. and 60 mmol of tert-butyl chloride (obtained from Sigma-Aldrich Chemie GmbH, Steinheim, Germany) were added at 22° C. The temperature was increased to 50° C. and the suspension was stirred for 60 minutes. Titanium(IV) chloride (0.15 mmol per gram of silica gel) obtained from Sigma-Aldrich Chemie GmbH, Steinheim, Germany and 30 ml of heptane were placed in a 250 mL four-necked round-bottomed glass flask and 33 mmol titanium(IV) isopropoxide (obtained from Sigma-Aldrich Chemie GmbH, Steinheim, Germany) were added dropwise within 10 minutes. The solution was stirred for 30 min, added to the suspension prepared above and stirred for 120 min at 50° C. The formed solid was isolated by filtration at 22° C. and then washed with heptane (500 ml) in three portions. The catalyst was dried under vacuum at 22° C. Yield: 442 g of a brown powder
99.2 g of the Ziegler catalyst component prepared in Example 2 were suspended in 300 mL of toluene. 2.98 mmol of the 2,6-bis[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine iron(II) dichloride prepared in Example 1 were dissolved in 94 mL of a 30 wt.-% solution of methylaluminoxane in toluene (corresponding to 446.5 mmol aluminum; obtained from Albemarle Corporation, Baton Rouge, USA) and stirred for 90 min. The dark brown solution was added dropwise to the suspension of the Ziegler catalyst component in toluene at 22° C. and the catalyst was thereafter stirred for 120 min at 22° C. The solid product was isolated by filtration at 22° C., washed with 200 mL of heptane and dried under vacuum at 22° C. for 2 hours. The mixed catalyst had an iron content of 30 μmol Fe per gram of Ziegler catalyst component prepared in Example 2.
Examples 3 was repeated except that 1.98 mmol of 2,6-bis[1-(2-chloro-4,6-dimethylphenylimino)ethyl]pyridine iron(II) dichloride dissolved in (62.5 mL of a 30 wt.-% solution of methylaluminoxane in toluene (corresponding to 297 mmol aluminum) were used. The mixed catalyst had an iron content of 20 μmol Fe per gram of catalyst.
Polymerization in Fluidized Bed Reactor
Polyethylenes suitable for preparing blow molded articles were prepared using the mixed catalyst systems prepared in Examples 3 and 4. The polymerization was carried out in a stainless steel fluidized bed reactor having an internal diameter of 200 mm equipped with a gas circulation system, cyclone, heat exchanger, control systems for temperature and pressure and feeding lines for ethylene, 1-hexene, nitrogen, hexane and hydrogen. The reactor pressure was controlled to be 2.4 MPa. The catalyst was injected in a discontinuous way by means of dosing valve with nitrogen at a rate of 1 g/h into the reactor. In addition, triisobutylaluminum (obtained from Chemtura Organometallics GmbH, Bergkamen, Germany) was added to the reactor in the amount indicated in Table 1. 12 ppm Costelan AS 100 obtained from H. Costenoble GmbH & Co. KG, Eschborn, Germany and 12 ppm Atmer 163 obtained from of Croda GmbH, Nettetal, Germany were metered into the reactor, where the amount of added Costelan AS 100 or Atmer 163 is specified as weight ratio to the produced polyethylene and feed of ethylene and 1-hexene in a ratio of 0.07 g of 1-hexene per g of ethylene was started.
When reaching steady state in the reactor, the reactor was discharging 5 kg/h of polyethylene. The hold-up in the reactor was controlled to be 15 kg, giving a mean residence time of 3 hours in the reactor. The discharged polymer powder was dried in a continuous way by flushing with nitrogen. 100 kg of each example were collected and pelletized in a Kobe LCM 50 extruder with a throughput of 57 kg/h and a specific energy of 0.260 kWh/kg. The reaction conditions in the polymerization reactor and the properties of the obtained pelletized polyethylenes are reported in Table 1.
The comparison between Examples 5 and 6 shows that by increasing the reactor temperature from 80° C. to 85° C. the activity of the Ziegler catalyst component is increased. Accordingly, the density and the number of vinyl groups decreases. Furthermore, since the polymer produced by the Ziegler catalyst component has a higher molecular weight, the values for MFR21.6 and MFR5 decrease. This can still be observed, especially for MFR21.6, although the amount of fed hydrogen was increased to compensate for that effect. Moreover, also the FRR decreases as a result of a narrower molecular weight distribution which also leads to a reduced swell ratio.
A similar behavior can be observed by comparing Examples 7 and 8, in which the reactor temperature was increased from 85° C. to 90° C.
Polyethylenes suitable for extruding pipes were prepared using the mixed catalyst system prepared in Example 3. The polymerization was carried out as in Examples 5 to 8. The reaction conditions in the polymerization reactor and the properties of the obtained polyethylenes are reported in Table 2; the characterization was however carried out using polyethylene powder.
The comparison of Comparative Examples A and B shows that by increasing the amount of fed hydrogen the molecular weight decreases, visible in higher values for values for MFR21.6 and MFR5, while the portion of the polyethylene obtained by polymerization from Ziegler catalyst component (B) decreases, which can be deduced from a higher number of vinyl groups and a slightly increased density since the comonomer incorporation of the Ziegler catalyst component (B) is higher than that of the late transition metal catalyst component (A). Furthermore, the molecular weight distribution is significantly reduced as shown by the FRR.
Examples 9, 10 and 11 prove that density, MFR5 and FRR can be kept constant by varying the temperature in combination with an amendment of the alky dosing and the hydrogen feed while the composition of the polyethylene is drastically changed. The comparison of Examples 9 to 10 shows that increasing the amount of alkyl increases the activity of the Ziegler catalyst component. (B). Even though the amount of fed hydrogen was increased to compensate mostly for that effect MFR21.6 and MFR5 increased. There was however no significant change in the composition of the polyethylene as can be seen from the constant number of vinyl groups and the molecular weight distribution was substantially narrower. By increasing the reactor temperature to 88° C. in Example 11 the proportion of the polyethylene obtained by polymerization by Ziegler component (B) was further increased and the loss in flowability compensated by increasing the hydrogen feed. FRR increased nearly to the value of Example 9 while density, MFR21.6 and MFR5 were very close to the values of Example 9. However, the composition of the polyethylene was significantly changed as can be observed in the lower number of vinyl groups and the different molecular weight distribution shown in
| Number | Date | Country | Kind |
|---|---|---|---|
| 10015962.3 | Dec 2010 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2011/073178 | 12/19/2011 | WO | 00 | 6/20/2013 |
| Number | Date | Country | |
|---|---|---|---|
| 61513235 | Jul 2011 | US |
