PROCESS TO PREPARE AN OLEFINE POLYMERIZATION CATALYST COMPONENT, CATALYST COMPONENT PARTICLES OBTAIN

专利摘要:
preparation of phthalate-free zn-pp catalysts the present invention relates to a new process for the preparation of new particulate olefin polymerization catalyst components, as well as the use of said new catalyst components to prepare a catalyst used in polymerization processes.
公开号:BR112014015791B1
申请号:R112014015791-0
申请日:2012-12-19
公开日:2021-03-30
发明作者:Peter Denifl；Timo Leinonen
申请人:Borealis Ag；
IPC主号:

专利说明:

[001] The present invention relates to a new process for the preparation of new particulate olefin polymerization catalyst components, as well as the use of said new catalyst components to prepare a catalyst used in polymerization processes. BACKGROUND OF THE INVENTION
[002] Polyolefin catalysts like Ziegler-Natta (ZN) are well known in the field of polymers, in general, they comprise (a) at least one catalyst component formed from a transition metal compound of group 4 to 6 of periodic table (IUPAC, Nomenclature of Inorganic Chemistry, 1989), a metallic compound from group 1 to 3 of the periodic table (IUPAC) and, optionally, a compound from group 13 of the periodic table (IUPAC) and / or an internal donor compound . The ZN type catalyst may also comprise (b) other catalyst component (s), such as a cocatalyst and / or an external donor.
[003] Various methods for preparing ZN-type catalysts are known in the art. In a known method, a supported ZN type catalyst system is prepared by impregnating the catalyst components onto a particulate support material. In WO-A-0155230, the catalyst component (s) is / are supported on a porous, inorganic or organic particulate carrier material, such as silica.
[004] In an additional well-known method, the carrier material is based on one of the catalyst components, for example, on a magnesium compound, such as MgCl2. This type of carrier material can also be formed in several ways. EP-A-713886, from Japan Olefins, describes the formation of the MgCl2 adduct with an alcohol which is then emulsified and, finally, the resulting mixture is suppressed to cause the drops to solidify.
[005] Alternatively, EP-A-856013 from BP discloses the formation of a solid Mg-based carrier, in which the phase containing the Mg component is dispersed to a continuous phase and the dispersed Mg phase is solidified by adding from a biphasic mixture to a liquid hydrocarbon.
[006] The solid carrier particles formed are usually treated with a transition metal compound and, optionally, with other compounds to form the active catalyst.
[007] In this sense, in the case of external carriers, some examples of which are disclosed above, the carrier morphology is one of the determining factors for the morphology of the final catalyst.
[008] A disadvantage found with supported catalyst systems is that the distribution of the catalytically active compounds on the support material is highly dependent on the support particle structure, such as the strength of the support particles, the porosity and the size distribution of the pores. As a result, this can often lead to non-uniform distribution of the active component (s) in the catalyst particle. As a consequence of the irregular distribution of the active sites in the catalyst, catalyst particles with intraparticle heterogeneities, as well as heterogeneities between particles between separate particles are obtained, which ultimately leads to a heterogeneous polymeric material.
[009] In addition, the support material will remain in the final polymer as a residue, which can be harmful in some polymer applications.
[010] WO-A-0008073 and WO-A-0008074 describe additional methods for the production of a ZN type catalyst, in which a solution of an Mg-based compound and one or more additional catalyst compounds are formed and the product of Its reaction is removed by precipitation of the solution by heating the system. In addition, EP-A-926165 discloses another precipitation method, in which a mixture of MgCl2 and Mg alkoxide is precipitated, together with a Ti compound to produce a ZN-type catalyst.
[011] According to US 2005/0176900, a magnesium compound, an alcohol, an ether, a surfactant and an alkyl silicate first react to obtain a catalyst support, which then reacts with a titanium compound. The solid titanium catalyst component is obtained by precipitation. The catalyst component further comprises an internal donor, which can be selected from a wide variety of compounds.
[012] WO 03/000757, as well as WO 03/000754, describe a process for the preparation of an olefin polymerization catalyst component, which allows to prepare solid particles of a catalyst component comprising a group 2 metal together with a metal of transition, however without using any external carrier material or using conventional precipitation methods, but using the so-called emulsification and solidification method for the production of solid catalyst particles. In this process, an internal phthalate electron donor is prepared in situ during the preparation of the catalyst in a way and using chemicals so that an emulsion is formed. The drops of the dispersed phase of the emulsion form the catalyst component and the solidification of the drops results in the solid particle catalyst.
[013] WO 2004/029112 discloses a further modification of the emulsion and solidification method, as described in WO 03/000757, as well as in WO 03/000754, and thus refers to the process for preparing a catalyst component of olefin polymerization, in which the process is additionally characterized by the fact that a specific aluminum alkyl compound is brought into contact with the catalyst component, allowing a certain degree of activity increase at higher temperatures.
[014] In this sense, although much development work in the field of Ziegler-Natta type catalysts has been done, there is still a need for alternative or improved methods of producing ZN type catalysts with desirable properties.
[015] Thus, it would be highly advantageous if a process for the preparation of olefin polymerization catalyst components was available, which would allow the formation of said solid catalyst components in different ways, such as through precipitation or by the emulsion method and solidification, depending on the desired properties of the catalyst particles, that is, morphology and / or desired particle size, whereby no gel-like material is formed during the preparation of the catalyst and, therefore, the produced catalyst results in the properties of the polymer desired, such as flow of molten material, soluble xylene content, etc. In the case of the production of random propylene-ethylene polymers, randomness is an essential characteristic that affects the properties of the polymer.
[016] Another aspect of the present invention is the desire to avoid, as far as possible, the use of substances that are considered compounds that are potentially harmful to health, as well as environmental aspects. A class of substances that have been considered to be potentially harmful compounds are phthalates, which have been commonly used as internal electron donors in Ziegler-Natta type catalysts. Although the amount of these phthalate compounds used as internal donors in catalysts, in the final polymer, is very small, it is still desirable to find alternative compounds to replace phthalate compounds and additionally obtain catalysts having good activity and excellent morphology, resulting in the desired properties of the polymer .
[017] The use of donors other than phthalate is not, as such, new in ZN type catalysts. However, such donors are used primarily in catalysts that are prepared by supporting the catalyst components in an external carrier. The disadvantages of such catalysts are described above.
[018] Until now, it has not been possible to form an emulsion just by changing a donor or donor precursor, due to the very sensitive nature of emulsion formation in this catalyst preparation method. Likewise, the precipitation behavior is significantly affected by the donor used, which influences the solubility of Mg compounds through the formation of an Mg complex.
[019] Thus, for both methods, the conditions for the formation of an emulsion respectively for precipitation depending on the chosen donor are not obvious to a person skilled in the art.
[020] It is therefore an object of the present invention to provide a catalyst component that has the desired chemical composition and particle size. In addition, the catalyst component has the desired morphology.
[021] It is therefore an additional object of the present invention to provide a method for the preparation of the solid catalyst components which allows the formation of the catalyst components in different ways (for example, by the precipitation or emulsion / solidification method), but with a common mechanism that does not yet require the use of phthalates as an internal electron donor, producing catalyst components of desired chemical composition, morphology and particle size, which are suitable for producing polymers with the desired polymer properties.
[022] Furthermore, it is an object of the invention to provide a catalyst, as described herein, for use in the polymerization of olefins.
[023] Surprisingly, these objects could be resolved by using an alcohol mixture comprising monohydric alcohol (A) and an alcohol (B) comprising, in addition to the hydroxyl portion, at least one ether portion during the preparation of the components of solid catalyst.
[024] It has been surprisingly found that the use of such an alcohol mixture during the preparation of the catalyst components produces catalysts that show a significant increase in catalytic activity compared to other ZN-type catalysts prepared without the use of such a mixture. Description of the invention
[025] Accordingly, the present invention provides the process for the preparation of an olefin polymerization catalyst component, as defined in claim 1.
[026] Thus, the present invention provides a process for preparing an olefin polymerization catalyst component in the form of solid particles, comprising the steps of (a1) providing a solution of at least one first alkoxy compound (Ax) being the product of the reaction of a group 2 metallic compound and a mixture of alcohol of a monohydric alcohol (A) of the formula ROH, with R being C6-C10 alkyl and an alcohol (B) comprising, in addition to the hydroxyl portion, at least an ether portion, optionally in an organic liquid reaction medium; or (a2) providing a solution of an alkoxy compound mixture of at least one first alkoxy compound (Ax) being the reaction product of a group 2 metal compound and a monohydric alcohol (A) of the formula ROH, with R being C6-C10 alkyl, optionally in a liquid organic reaction medium and at least a second alkoxy compound (Bx) the reaction product being a group 2 metal compound and an alcohol (B) comprising, in addition to the hydroxyl moiety, at least an ether portion, optionally in an organic liquid reaction medium; and (b) adding said solution to at least one transition metal compound and (c) preparing the solid catalyst component particles, wherein an internal electron donor selected from benzoates, alkylene glycol dibenzoates, maleates, dialkylester 1- cyclohexene-1,2-dicarboxylic and 1,3-diethers, or a mixture of any selected donors or a corresponding precursor is added to any step prior to step (c).
[027] Preferred modalities are described in the dependent claims, as well as in the description below. In addition, the present invention provides the catalyst components obtainable according to the present invention and also the use of the catalyst components in the polymerization of olefins.
[028] The invention will be described in more detail below, with reference to specific preferential modalities. It is essential in all modalities that the solid catalyst can be prepared through the solidification method of the liquid-liquid biphasic system (emulsion) or through the precipitation method, without the need to use phthalate compounds that produce catalyst particles with physical properties. desired morphological properties and / or desired particle size and particle size distribution especially desired.
[029] It has been surprisingly found by the inventors of the present invention that the particles of the catalyst component having in the modalities the desired morphology and / or particle size and / or particle size distribution and high activity can be obtained by preparation, by emulsion-solidification or precipitation, of the Ziegler-Natta (ZN) catalysts, which are suitable for use in the polymerization of olefins, in particular for the polymerization of propylene, but without requiring the use of phthalates. According to the replication effect, the polymer particles produced using the catalyst of the invention also have desired morphological properties.
[030] The preparation of the catalyst of the invention is based on a two-phase liquid / liquid system (emulsion / solidification method) or on a precipitation method where no separate external carrier material, such as silica or MgCl2, is necessary in order to obtain solid catalyst particles.
[031] This process for preparing solid catalyst particles is in particular characterized by the fact that the formation of the catalyst component comprises a1) using at least one alkoxy compound (Ax) being the reaction product of at least one group 2 metallic compound and a mixture of alcohol of a monohydric alcohol (A) and an alcohol (B) comprising, in addition to the hydroxyl portion, at least one ether portion or a2) use an alkoxy compound mixture at least one alkoxy compound (Ax) being the product of reaction of at least one group 2 metal compound and a monohydric alcohol (A) and an alkoxy compound (Bx) being the reaction product of a group 2 metal compound and an alcohol (B) comprising, in addition to the hydroxyl portion, at least one ether portion and additionally characterized by the fact that the phthalate-free internal electron donor is used in the preparation of the catalyst as such or formed in situ.
[032] Especially preferred is variant (a2) using mixtures of alkoxy compound.
[033] The alkoxy compounds (Ax and Bx) can be prepared in situ in the first stage of the catalyst preparation process by reacting said group 2 metal compounds with the alcohol or alcohol mixture, as described above, or said compounds alkoxy can be reaction products prepared separately, or they can even be commercially available as ready-made compounds and used as such in the catalyst preparation process of the invention.
[034] During the preparation of the alkoxy compounds (Ax or Bx) from at least one group 2 metal compound and the alcohol or alcohol mixture, as defined above, a donor or a donor precursor can be added to the reaction mixture, whereby a group 2 metal complex (an Ac or Be complex) is formed, which is defined in that application as being a complex of at least the group 2 metal compound, the alcohol or the alcohol mixture and a donor.
[035] If the alkoxy compounds (Ax) and / or (Bx) are formed without using any / any donor (s) or donor precursor (s), the donor (s) as such are / are added separately to the solution of the reaction product or during the preparation of the catalyst component.
[036] Group 2 metal compounds are selected from the group comprising, preferably consisting of group 2 metal dialkyls, group 2 metal alkoxides, group 2 metal alkyl halides and group 2 metal dihalides They can be further selected from the group consisting of group 2 metal dialkyloxy, group 2 metal diaryloxy, group 2 metal alkyloxides, group 2 metal aryloxide halides, group 2 metal alkyl alkoxides , group 2 metal aryl alkoxides and group 2 metal alkyl aryloxides. Preferably, the group 2 metal is magnesium.
[037] Monohydric alcohols (A) are those of the formula ROH in which R is a straight or branched C6-C10 alkyl group, preferably a branched C6 alkyl group.
[038] Preferred monohydric alcohols include hexanol, 2-ethyl-1-butanol, 4-methyl-2-pentanol, 1-heptanol, 2-heptanol, 4-heptanol, 2,4-dimethyl-3-pentanol, 1 -octanol, 2-octanol, 2-ethyl-1-hexanol, 1-nonanol, 5-nonanol, diisobutylcarbinol, 1-decanol and 2,7-dimethyl-2-octanol. The most preferred monohydric alcohol is 2-ethyl-1-hexanol.
[039] Alcohol (B) comprising at least one ether moiety is an aliphatic compound. The aliphatic compounds can be linear, branched or cyclic, or any combination thereof, and particular preferred alcohols are those that comprise only one ether moiety.
[040] Illustrative examples of such a preferred ether portion containing alcohols (B) to be employed according to the present invention are glycolic monoethers, in particular C2 to C4 glycolic monoethers, such as ethylene or propylene glycol monoethers, wherein the ether moieties comprise 2 to 18 carbon atoms, preferably 2 to 12 carbon atoms and, more preferably, 2 to 8 carbon atoms. Preferred monoethers are C2 to C4 glycolic monoethers and their derivatives. Illustrative and preferred examples are ethylene glycol butyl ether, ethylene glycol-hexyl ether, ethylene glycol-2-ethylhexyl ether, propylene glycol-n-butyl ether, propylene glycolmethyl ether, propylene glycol ethyl ether, propylene glycol ether-2-hexyl-ethylene-hexane , with ethylene glycol-hexyl ether, 1,3-propylene glycolethyl ether and 1,3-propylene glycol-n-butyl ether being particularly preferred.
[041] The most preferred alcohols (B) are 1,3-propylene glycolethyl ether and 1,3-propylene glycol-n-butyl ether.
[042] Generally, the different alkoxy compounds or alcohols are used in a 10: 1 to 1:10 molar ratio, preferably this molar ratio is 8: 1 to 1: 8, more preferably 6: 1 to 1: 6 , even more preferably from 5: 1 to 1: 5 and, in modalities also 4: 1 to 1: 4 or even 2: 1 to 1: 2. This ratio can be adjusted depending on the donor used, for example, donors with short chains require longer chain alcohols and vice versa.
[043] The reaction for the preparation of the alkoxy compounds (Ax) and (Bx) can, in modalities, be carried out preferably in an aromatic or aromatic / aliphatic medium at a temperature of 20 ° C to 80 ° C and, in the case that the Group 2 metal is magnesium, the preparation of the alkoxymagnesium compound can be carried out at a temperature of 50 ° to 70 ° C.
[044] The reaction medium used as a solvent can be aromatic or a mixture of aromatic and aliphatic hydrocarbons, the latter containing 5 to 20 carbon atoms, preferably 5 to 16 carbon atoms, more preferably 5 to 12 carbon atoms and, more preferably 5 to 9 carbon atoms. Preferably, the aromatic hydrocarbon comprises selected substituted and unsubstituted benzenes, preferably alkylated benzenes, even more preferably toluene and xylenes, and is most preferably toluene.
[045] The molar ratio of said reaction medium to magnesium is preferably less than 10, for example, from 4 to 10, preferably from 5 to 9.
[046] The alkoxy compounds (Ax) and (Bx) are preferably alkoxymagnesium compounds.
[047] The alkoxymagnesium compound group is preferably selected from the group consisting of magnesium dialoxides, magnesium dihalide complexes and an alcohol and magnesium dihalide complexes and a dialkoxide, or mixtures thereof. Most preferably, the alkoxymagnesium compound is a dialkoxymagnesium compound.
[048] The alkoxymagnesium compound is the product of the reaction of an alcohol (A), respectively alcohol (B) or a mixture of alcohol (A) and alcohol (B) with a magnesium compound selected from the group consisting of dialkylmagnesiums, alkoxides alkyl magnesium, alkyl magnesium halides and magnesium dihalides. It can be further selected from the group consisting of dialkoxymagnesiums, diaryloxymagnesiums, alkyloxymagnesium halides, aryloxymagnesium halides, alkylmagnesium alkoxides, arylmagnesium alkoxides and alkylmagnesium aryloxides.
[049] The dialkoxymagnesium is preferably the product of the dialkylmagnesium reaction of formula R2Mg, where each of the two Rs is a similar or different C1-C20 alkyl, preferably a similar or different C2-C10 alkyl, and alcohol (A) and / or (B).
[050] Typical alkyl magnesium are ethyl butyl magnesium, dibutyl magnesium, dipropyl magnesium, propyl butyl magnesium, dipentyl magnesium, butyl pentyl magnesium, butyl butyl magnesium and dioctyl magnesium. More preferably, one R of the formula R2Mg is a butyl group and the other R is an ethyl or octyl group, that is, the dialkylmagnesium compound is butyloctymagnesium or ethylbutylmagnesium.
[051] RMgOR alkylalkoxymagnesium compounds, when used, are ethylmagnesium butoxide, butylmagnesium pentoxide, octylmagnesium butoxide and octylmagnesium octoxide.
[052] More preferably, the alkoxy compound (Ax) is obtained by the reaction of dialkylmagnesium of the formula R2Mg, with R being a different C2-C8 alkyl, even more preferably by the reaction of butyloctylmagnesium or ethylbutylmagnesium with 2-ethylhexanol and o alkoxy compound (Bx) is obtained by the reaction of dialkylmagnesium of formula R2Mg, with R being a different C2-C8 alkyl, even more preferably by the reaction of butyloctylmagnesium or ethylbutylmagnesium with a C2 or C3 alkylglycolic alkyl ether, even more preferably with 1,3-propylene glycolethyl ether or 1,3-propylene glycol-n-butyl ether, whereby the molar ratio of monohydric alcohol (A), such as 2-ethylhexanol to alcohol (B) as ether 1.3 -propylene glycolethyl or 1,3-propylene glycol-n-butyl ether is in the range of 6: 1 to 1: 6, preferably from 5: 1 to 1: 5 and more preferably from 4: 1 to 1: 4.
[053] The phthalate-free electron donor compound used in the preparation of the catalyst of the present invention is preferably selected from benzoates, alkylene glycolibenzoates, maleates, dialkylester 1-cyclohexene-1,2-dicarboxylic and 1,3-diethers, or mixtures of the same.
[054] Preferably, phthalate-free internal donors are selected from: a) benzoates of formula (I)
with R being a straight or branched C1-C12 alkyl group, preferably a straight or branched C2-C10 alkyl group, more preferably a straight or branched C4-C9 alkyl group, and more preferably a branched C6-C8 alkyl group, such as 2- ethylhexyl, and R 'being H or a straight or branched C1-C12 alkyl group, preferably a straight or branched C2-C10 alkyl group, more preferably a straight or branched C4-C8 alkyl group, such as tert-butyl or n- hexyl, whereby the alkyl group may contain one or more heteroatoms selected from O, N or S, preferably O or N, more preferably O, in the alkyl chain, or may be substituted by one or more substituents selected from de = O, halogen, such as chlorine, fluorine or bromine, or optionally substituted C6-C14 aryl.
[055] The C6-C14 aryl group is preferably a phenyl group, the optional substituents on the aryl group can be straight or branched C1-C12 alkyl, preferably straight or branched C1-C10 alkyl and, more preferably, linear or C1-C8 alkyl branched or halogen, such as chlorine, fluorine or bromine, and more preferably chlorine. The number of substituents on the aryl group can be from 0 to 4, preferably from 0 to 2, more preferably 0 or 1.
[056] R 'other than H may be in the ortho, meta or to position, preferably in the para or ortho position.
[057] Most preferred compounds are 2-ethylhexyl benzoate, 2-ethylhexyl (4-n-hexylbenzoate), 2-ethylhexyl (4-tert-butylbenzoate) and ((2- (4- chlorobenzoyl) 2-ethylhexyl benzoate) .b) Alkylene glycol dibenzoates of formula (II)
with n being 1 or 2, if n = 1, then R = CH3 and if n = 2, then R = H.
[058] Most preferred compounds are ethylene glycol dibenzoate, 1,2-propylene glycol dibenzoate 1,3-propylene glycol dibenzoate.c) maleates of formula (III)
with R1 and R2 being the same or different and being a straight or branched C1-C12 alkyl group, preferably a straight or branched C1-C8 alkyl group, more preferably a straight or branched C1-C4 alkyl group and more preferably ethyl, by means of R1 and R2 are preferably the same and with R being H or a linear, branched or cyclic C1 to C12 alkyl, preferably a branched or cyclic C3 to C8 alkyl, such as iso-butyl, cyclopentyl or cyclohexyl, whereby it is preferable that R is not H.
[059] Most preferred compounds are diethyl-2-isobutyl maleate, diethyl-2-cyclopentyl maleate and diethyl-2-cyclohexyl maleate.d) dialkylester 1-cyclohexene-1,2-dicarboxylic formula ( IV)
with R1 and R2 may be identical or different and may be a straight or branched C1-C20 alkyl, preferably a straight or branched C2-C16 alkyl and, more preferably, a straight or branched C5-C12 alkyl. Preferably, R1 and R2 are identical.
[060] The most preferred compound is 1-cyclohexene-1,2- (bis- (2-ethylhexyl) dicarboxylate.e) 1,3-diethers of formula (V) or (VI)

[061] R1 and R2 are the same or different and can be straight or branched C1-C12 alkyl, or R1 with R5 and / or R2 with R6 can form a ring with 4 to 6 C atoms,
[062] R3 and R4 of formula (V) are the same or different and can be H or a straight or branched C1-C12 alkyl, or R3 and R4 can together form a ring with 5 to 10 C atoms that can be part of an aliphatic or aromatic polycyclic ring system with 9 to 20 C atoms,
[063] R5 and R6 in formula (V) are the same or different and can be H or a straight or branched C1-C12 alkyl or can form together an aliphatic ring with 5 to 8 C atoms, and R51, R61 and R7 in formula (VI) are the same or different and can be H or a straight or branched C1-C12 alkyl or two or three of R51, R61 and R7 can form, together with C1 to C3, an aromatic ring or ring system with 6 to 14 C atoms, preferably 10 to 14 C atoms.
[064] R1 and R2 are preferably the same in formula (V) and (VI), and can be a straight or branched C1-C10 alkyl, more preferably C1-C8 alkyl, such as methyl, ethyl, n-propyl, i-propyl , n-butyl or tert-butyl or 2-ethylhexyl.
[065] In formula (V) it is still possible that R1 with R5 and / or R2 with R6 can form, together with the oxygen atom, a ring with 4 to 6 C atoms, preferably 4 to 5 C atoms, as a tetrahydrofuran ring or a tetrahydropyran ring.
[066] R3 is preferably a straight or branched C1-C10 alkyl, more preferably a C1-C9 alkyl, such as methyl, ethyl, i-propyl, i-butyl or n-nonyl.
[067] R3 is preferably H a straight or branched C1-C10 alkyl, more preferably a C1-C6 alkyl, such as methyl, i-propyl, n-butyl, i-butyl or i-pentyl.
[068] It is also possible that R3 and R4 can form a ring together, preferably an alicyclic ring preferably with 5 to 7 C atoms, more preferably 5 to 6 C atoms, such as cyclopentane, 2 or 3-cyclopentene, cyclohexene or 2, 3 or 4-cyclohexene.
[069] It is still possible that this ring is part of an alicyclic or aromatic polycyclic ring system with 9 to 18 C atoms, such as decalin, hydroindane, fluorene or indane.
[070] R5 in formula (V) can preferably be H or a straight or branched C2-C6 alkyl, more preferably it can be H or C2-C6 alkyl and, more preferably, H.
[071] R6 in formula (V) can preferably be H or a straight or branched C2-C8 alkyl, preferably H or a linear C3-C6 alkyl, such as i-propyl or i-butyl.
[072] In formula (V), it is still possible that R5 and R6 can form together an aliphatic ring with 5 to 8 C atoms, such as cyclopentane, cyclohexene or cycloheptane.
[073] In formula (VI), R51, R61 and R7 are the same or different and are preferably H or a straight or branched C1-C10 alkyl, more preferably H or a straight or branched C1-C8 alkyl like methyl, i -propyl, n-butyl, i-butyl and i-pentyl.
[074] In formula (VI), it is still possible for two or three groups R51, R61 and R7 to form, together with C1 to C3, an aromatic ring or ring system with 6 to 14 C atoms, preferably 10 to 14 atoms C. Such aromatic rings or ring systems are phenyl, naphthalene, anthracene or phenanthrene. Preferably, such a ring system is naphthalene.
[075] Most preferred compounds are 1,8-bis (2-ethylhexyloxy) naphthalene, 3,3-bis (ethoxymethyl) -2-methyldodecane and 3,3-bis (ethoxymethyl) -2,6-dimethylheptane .
[076] Most preferably, phthalate-free internal donors are selected from ethylene glycol dibenzoate, 1,2-propylene glycol dibenzoate and 1,3-propylene glycol dibenzoate, diethyl-2-isobutyl maleate, diethyl-2-cyclopentyl maleate and diethyl-2-cyclohexyl maleate, or mixtures thereof.
[077] The transition metal compound is preferably a group 4 metal compound. The group 4 metal is preferably titanium, and its compound to be reacted with the group 2 complex is preferably a halide. Equivalent to titanium tetrahalide is the combination of an alkoxytitanium halide and a halogenating agent thereof, which are capable of forming a titanium tetrahalide on the spot. The most preferred halide is chloride.
[078] In another embodiment of the invention, a transition metal compound used in the process can also contain organic binders normally used in the field known as a single site catalyst.
[079] In yet a further embodiment of the invention, a transition metal compound can also be selected from group 5 metal compounds, group 6 metals, Cu, Fe, Co, Ni and / or Pd.
[080] In principle, said components of olefin polymerization catalyst can be obtained in several ways, all based on the same mechanism.
[081] In one embodiment, the preparation of the catalyst component in the form of solid particles comprises the steps of (a1) (a1-1) providing a solution (S1) of at least one first alkoxy compound (Ax) being the product of the reaction of a group 2 metal compound and a mixture of alcohol of a monohydric alcohol (A) of the formula ROH, with R being C6-C10 alkyl and an alcohol (B) comprising, in addition to the hydroxyl moiety, at least one ether moiety , optionally in an organic liquid reaction medium, or (a1-2) providing a solution (S1) of an alkoxy compound mixture of at least one first alkoxy compound (Ax) being the reaction product of a group 2 metal compound and a monohydric alcohol (A) of the formula ROH, with R being C6-C10 alkyl, optionally in a liquid organic reaction medium and at least a second alkoxy compound (Bx) being the reaction product of a group 2 metal compound and an alcohol (B) comprising, in addition to the hydroxyl portion, at least one ether portion, optionally in an organic liquid reaction medium; and an internal donor as described above, or a mixture thereof, or a precursor thereof in an organic liquid reaction medium; and (b1) combining said solution (S1) with at least one transition metal compound (CT), (c1) precipitating said catalyst component as a solid particle, and (d1) recovering the solidified particles of the component olefin polymerization catalyst.
[082] In step (a1), it is possible to use an alkoxy compound (Ax) being a reaction product of at least one group 2 metallic compound and a mixture of alcohol (A) with alcohol (8) as defined above, ( a1-1)
[083] The second possibility (a1-2) is to use a mixture of an alkoxy compound (Ax) being a reaction product of at least one group 2 metal compound and a monohydric alcohol (A) and an alkoxy compound ( Bx) being a reaction product of at least one group 2 metallic compound and an alcohol (B), as defined above.
[084] The possibility (a1-2) is preferred.
[085] It is possible to dissolve the transition metal compound (CT) in step (b1) in an organic liquid reaction medium (OM2), through which the solution (S2) is formed.
[086] The process of precipitation of solids can be carried out by several methods:
[087] In one embodiment, the addition of the solution (S1) to at least one transition metal compound (CT) in step (b1) is done at a temperature of at least 50 ° C, preferably in the temperature range of 50 ° C. at 110 ° C, more preferably in the range of 70 to 100 ° C, more preferably in the range of 85 to 95 ° C, at whose temperature the at least one transition metal compound (CT) is in liquid form, resulting in precipitation of said solid catalyst components.
[088] In this case, it is especially estimated that after combining the solution (S1) with at least one transition metal compound, the entire reaction mixture is kept at least 50 ° C, most preferably it is kept in the temperature range of 50 to 110 ° C, more preferably in the range of 70 to 100 ° C, more preferably in the range of 85 to 95 ° C, to ensure complete precipitation of the catalyst component in the form of a solid particle.
[089] In this case, it is possible for a surfactant to be added in step (a1) or in step (b1).
[090] General examples of surfactants include polymeric surfactants, such as (poly) alkyl methacrylate and (poly) alkyl acrylate, and the like. A (poly) alkyl methacrylate is a polymer that can contain one or more methacrylate monomers, such as at least two different methacrylate monomers, at least three different methacrylate monomers, etc. In addition, acrylate and methacrylate polymers may contain monomers other than acrylate and methacrylate monomers, provided that the polymeric surfactant contains at least about 40% by weight of acrylate and methacrylate monomers.
[091] Examples of surfactants that are commercially available include those under the commercial VISCOPLEX® cabinets, available from RohMax Additives, GmbH, especially those that have the product designations 1254, 1-256 and those under the trade names CARBOPOL® and PEMULEN ®, available from Noveon / Lubrizol.
[092] In a second embodiment, the solution (S1) is mixed with at least one transition metal compound (CT) in liquid form at a temperature of -20 ° C to about 30 ° C and precipitation of the components of solid catalysts by the subsequent reduction in the rate of temperature rise to at least 50 ° C, preferably in the range of 50 to 110 ° C, more preferably in the range of 70 to 100 ° C, more preferably in the range of 85 to 95 ° C, for example means that the rate of temperature increase is in the range of 0.1 ° C to 30 ° C per minute, preferably 0.5 to 10 ° C per minute.
[093] In this case, it is especially estimated that a surfactant is added to the solution (S1) before step (b1). Appropriate surfactants are described above.
[094] In both cases it is possible, but not necessary, to add a certain amount of precipitating agent to the system. Such precipitation agents are capable of affecting the morphology of the particles formed during the precipitation stage. In a specific process, no precipitation agent was used. A precipitation agent according to this invention is an agent that promotes the precipitation of the catalyst component in the form of a solid particle. The organic liquid medium used as (OM2), as defined later in this application, can promote precipitation and thus act and be used as a precipitating agent. However, the final catalyst does not contain any such means.
[095] In addition, it is preferable that no precipitating agent is used in the process, as indicated above.
[096] Preferably, the catalyst component, as prepared in the previous paragraphs, is a precipitated solid particle.
[097] "Precipitation", according to this invention, means that during the preparation of the catalyst component, a chemical reaction in solution occurs producing the desired insoluble catalyst component in said solution.
[098] Suitable alkoxy compounds (Ax) and (Bx) and their preparation have been described above.
[099] Suitable electron donors and their precursors, as well as transition metal compounds are also described above.
[100] Preferably, TiCl4 is used as a transition metal compound.
[101] If the electron donor is used as such, it is added to the alkoxy compound (Ax) or alkoxy compound (Bx), whereby the reaction medium used as a solvent for the group 2 metal compound can be aromatic or a mixture of aromatic and aliphatic hydrocarbons, the latter containing 5 to 20 carbon atoms, preferably 5 to 16 carbon atoms, more preferably 5 to 12 carbon atoms and, most preferably, 5 to 9 carbon atoms. Preferably, the aromatic hydrocarbon is selected from substituted and unsubstituted benzenes, preferably from alkylated benzenes, even more preferably from toluene and xylenes, and is most preferably toluene.
[102] The electron donor can also be introduced in the form of a precursor, as described above, which is then transformed in situ into the electron donor by reacting with a corresponding Mg alkoxide. Mg alkoxide is prepared as described above by reacting a magnesium compound with the corresponding alcohol (A) or alcohol (B).
[103] Additional donors can be added, if desired, in the preparation of the catalyst in any of steps (a1) to (b1). Preferably the additional donors, if used, are likewise esters of non-phthalic acid.
[104] It is also possible to use mixtures from the donors described above.
[105] The reaction medium corresponds to the organic liquid reaction medium (OM1) of step (a1).
[106] The organic liquid reaction medium (OM2), where TiCl4 can be separated, can be the same as the organic liquid reaction medium (OM1) or can be different, the latter being preferred.
[107] Preferably, the organic liquid reaction medium (OM2) is C5 to C10 hydrocarbon, more preferably from a C10 alkane, such as heptane, octane or nonane, or any mixtures thereof.
[108] It is particularly estimated that the organic liquid reaction medium (OM1) is a C10 aromatic hydrocarbon, more preferably toluene, and the organic liquid reaction medium (OM2) is a C10 alkane, more preferably heptane.
[109] In addition, it is estimated that the organic liquid reaction media (OM1) and (OM2) are selected in a way that supports immediate precipitation of the solid catalyst particle.
[110] When adding the solution (S1) to at least one transition metal (CT) compound, the mixture is estimated. Suitable mixing techniques include the use of mechanics, as well as the use of ultrasound to mix, as is known to the person skilled in the art.
[111] After precipitation, the solid catalyst particle is washed in a known manner.
[112] It is therefore preferred that the solid catalyst particle is washed at least once up to 6 times, preferably at least twice, more preferably at least three times with a hydrocarbon, which is preferably selected from aromatic and aliphatic hydrocarbons, preferably with toluene, heptane or pentane, more preferably toluene, particularly with hot toluene (for example, from 80 to 100 ° C), which can include a greater or lesser amount of TiCl4 in it. The amount of TiCl4 can vary from a few% by volume to more than 50% by volume, as from 5% by volume to 50% by volume, preferably from 5 to 15% by volume. It is also possible that at least one wash is done with 100% by volume of TiCl4.
[113] One or more additional washings after washing with TiCl4 and / or aromatics can be performed with aliphatic hydrocarbons of 4 to 8 carbon atoms. Preferably, these last two washes are carried out with heptane and / or pentane. Washes can be done with hot hydrocarbons (for example, 90 ° C) or cold (room temperature), or combinations of them. It is also possible that all washes are done with the same solvent, for example, toluene.
[114] In addition, during the preparation of the catalyst component, a reducing agent, which decreases the amount of titanium present in said solidified particles of the olefin polymerization component being present in the +4 oxidation state, can be added.
[115] Suitable reducing agents are alkyl aluminum compounds, alkyl alkoxy aluminum compounds and magnesium compounds, as defined in this specification.
[116] Suitable aluminum compounds have a general formula AlR3-nXn, where R represents a straight or branched chain alkyl or alkoxy group having from 1 to 20, preferably from 1 to 10 and, more preferably, from 1 to 6 atoms of carbon, X independently represents a residue selected from the halogen group, preferably chloride, and n represents 0, 1 or 2. At least one of the residues R must be an alkyl group.
[117] The compound can be added as an optional compound for the synthesis of the catalyst component, and can be added at any step (b1) to (c1) or during the washing step as described above, however, before step ( d1).
[118] Preferably, the reducing compound is added during the washing step, more preferably during the first washing step with hot toluene.
[119] Illustrative examples of alkyl and alkoxyaluminium compounds to be used according to the present invention are:
[120] Chlorinated trialkyl (C1-C6) -aluminum compounds and aluminum (C1-C6) compounds, especially diethylaluminium chloride; diethyl aluminum ethoxide, ethyl aluminum dioxide, diethyl aluminum methoxide, diethyl aluminum propoxide, diethyl aluminum butoxide, dimethyl aluminum ethoxide, of which, in particular, diethyl aluminum ethoxide is preferred.
[121] Suitable magnesium compounds are magnesium compounds, as defined herein, attached to a group 2 metal complex. The respective disclosure is incorporated into the present invention by reference to the magnesium compound to be added according to process of the present invention. In particular, suitable magnesium compounds are dialkylmagnesium compounds or halogenated alkylmagnesium compounds of the general formula MgR2-nXn, where each n is 0 or 1, and each R is the same or different alkyl groups having 1 to 8 carbon atoms and X is halogen, preferably Cl. A preferred magnesium compound is butyloctylmagnesium (commercially available under the trade name BOMAG), which is already preferentially used in the preparation of the Mg complex.
[122] The amount of optional compound A1 added depends on the desired degree of reduction of the titanium present in solidified particles of the olefin polymerization catalyst component present in the +4 oxidation state. Preferred amounts of Al in the catalyst component depend to some extent on the compound Al, for example, if an alkoxy compound of Al is used, the preferred final amounts of Al appear to be less than if, for example, chloride compounds alkyl aluminum are used.
[123] The particles of the final catalyst component have an Al content of 0.0 to 0.8 wt%, preferably 0.0 to 0.5 wt% or 0.0 to 0.4 wt% .
[124] The magnesium compound to be added according to the present invention is added in corresponding amounts.
[125] Preferably, a chlorinated alkyl aluminum compound, especially diethyl aluminum chloride, is added.
[126] In the second embodiment, the preparation of the catalyst component in the form of solid particles comprises the steps of (a2) (a2-1) providing a solution (S1) of at least one first alkoxy compound (Ax) being the product of the reaction of a group 2 metal compound and a mixture of alcohol of a monohydric alcohol (A) of the formula ROH, with R being C6-C10 alkyl and an alcohol (B) comprising, in addition to the hydroxyl moiety, at least one ether moiety , optionally in an organic liquid reaction medium, or (a2-2) providing a solution (S1) of an alkoxy compound mixture of at least one first alkoxy compound (Ax) being the reaction product of a group 2 metal compound and a monohydric alcohol (A) of the formula ROH, with R being C6-C10 alkyl, optionally in a liquid organic reaction medium and at least a second alkoxy compound (Bx) being the reaction product of a group 2 metal compound and an alcohol (B) comprising, in addition to the hydroxyl portion, at least one ether portion, optional in an organic liquid reaction medium; and an internal donor as described above, or a mixture thereof, or a precursor thereof in an organic liquid reaction medium, (b2) adding said solution (S1) to at least one transition metal compound to produce an emulsion , the phase of which is in the form of drops and contains more than 50 mol% of the group 2 metal in the alkoxy compound, (c2) stir the emulsion to keep the drops of said phase dispersed in said predetermined average size range from 2 to 500 μm, (d2) solidify said drops of the dispersed phase, (e2) recover the solidified particles of the olefin polymerization catalyst component.
[127] In step (a2), it is possible to use an alkoxy compound (Ax) being a reaction product of at least one group 2 metallic compound and a mixture of alcohol (A) with alcohol (B) as defined above. (a2-1).
[128] The second possibility (a2-2) is to use a mixture of an alkoxy compound (Ax) being a product of the reaction of at least one group 2 metal compound and a monohydric alcohol (A) and an alkoxy compound ( Bx) being a reaction product of at least one group 2 metallic compound and an alcohol (B), as defined above.
[129] The possibility (a2-2) is preferred.
[130] Suitable alkoxy compounds (Ax) and (Bx) and their preparation have been described above.
[131] Suitable electron donors and their precursors, as well as transition metal compounds are also described above.
[132] The internal donor, or its precursor, as defined above, is preferably added in step (a2) to the alkoxy compound (Ax) of the possibility (a2-1) or to the alkoxy compound (Ax) or (Bx) of possibility (a2-2). The solution (S1) of step (a2) is then typically added to at least one transition metal compound, such as titanium tetrachloride. This addition is preferably carried out at a low temperature, such as from -10 to 40 ° C, preferably from -5 to 30 ° C, as from about 0 ° C to 25 ° C.
[133] During any of these steps, a reaction medium or organic solvent may be present, usually selected from aliphatic and / or aromatic hydrocarbons, as described above.
[134] Additional donors can be added, if desired, in the preparation of the catalyst in any of the steps (a2) through (c2). Preferably the additional donors, if used, are likewise esters of non-phthalic acid.
[135] It is also possible to use mixtures of the mixtures described above.
[136] The process according to the present invention provides an intermediate stage, as identified above an emulsion of a dispersed oily phase insoluble in toluene / denser transition metal compound, typically with a transition metal / metal molar ratio of group 2 from 0.1 to 10 in a phase dispersed in oil, with a transition metal / metal ratio of group 2 from 10 to 100.
[137] The transition metal compound is preferably a group 4 metal compound, and is most preferably TiCl4. Preferably, the group 2 metal is Mg. That emulsion is then typically agitated, optionally in the presence of an emulsion stabilizer and / or a turbulence-minimizing agent, in order to keep the drops of said dispersed phase typically within an average size range of 5 to 500 μm. The catalyst particles are obtained after solidification of said particles of the dispersed phase, for example, by heating.
[138] The dispersed and dispersed phases are thus distinguishable from each other by the fact that the denser oil, if it comes in contact with a solution of the group 4 metal compound, preferably TiCl4 in toluene, will not dissolve in it. A suitable solution to define this criterion would be to have a toluene molar ratio of 0.1 to 0.3. They are also distinguishable by the fact that the large preponderance of the supplied Mg (as a complex) for the reaction with the group 4 metal compound is present in the dispersed phase, as revealed by comparing the respective group 4 / Mg metal molar ratios.
[139] In effect, therefore, practically the entire product of the reaction of the Mg complex with the group 4 metal - which is the precursor of the final catalyst component - becomes the dispersed phase and proceeds through additional processing steps until the final particulate form. The dispersed phase, still containing a useful amount of group 4 metal, can be reprocessed to recover the metal.
[140] The production of the biphasic reaction product is encouraged by carrying out the Mg complex / group 4 metal compound reaction at low temperature, specifically above -10 ° C, but below 50 ° C, preferably between above - 5 ° C and below 40 ° C. Since the two phases will naturally tend to separate into a lower, denser phase, and in the lighter supernatant phase, it is necessary to keep the reaction product as an emulsion by stirring, preferably in the presence of an emulsion stabilizer.
[141] The emulsion, that is, the biphasic liquid-liquid system, can be formed in all the modalities of the present invention by simple stirring and, optionally, adding more solvent (s) and additives, such as a turbulence-minimizing agent (TMA) and / or the emulsifying agents described below.
[142] Emulsion emulsifying / stabilizing agents may additionally be used in a manner known in the art to facilitate the formation and / or stability of the emulsion. For said purposes, for example, surfactants, for example, a class based on acrylic or methacrylic polymers can be used. Preferably, said emulsion stabilizers are acrylic or methacrylic polymers, especially those with medium-sized ester side chains with more than 10, preferably more than 12 carbon atoms and, preferably, less than 30 and preferably 12 to 20 atoms carbon in the ester side chain. Particularly preferred are unbranched C12 to C20 (meth) acrylates, such as (poly) hexadecyl methacrylate and (poly) octadecyl methacrylate. Suitable examples of commercially available surfactants are, for example, those sold under the name Viscoplex®, such as Viscoplex®, 1-124 and 1-126, as indicated earlier in this application.
[143] As mentioned above, a turbulence-minimizing agent (TMA) can be added to the reaction mixture to improve emulsion formation and maintain the structure of the emulsion. Said TMA agent must be inert and soluble in the reaction mixture under the reaction conditions, which means that polymers without polar groups are preferred, as polymers with linear or branched aliphatic carbon chains.
[144] Said TMA is, in particular, preferably selected from alpha-olefin polymers and alpha-olefin monomers with 6 to 20 carbon atoms, such as polyoctene, polynonene, polydecene, polyundecene or polydodecene, or mixtures thereof. Most preferably, it is polydecene. TMA can be added to the emulsion in an amount, for example, from 1 to 1,000 ppm, preferably from 5 to 100 ppm and, more preferably, from 5 to 50 ppm, based on the total weight of the reaction mixture.
[145] It was found that the best results are obtained when the metal molar ratio of group 4 / Mg of the densest oil is 1 to 5, preferably 2 to 4, and that the oil in the dispersed phase is 55 to 65.
[146] Generally, the molar ratio of the group 4 metal / Mg in the oil of the dispersed phase in the denser oil is at least 10.
[147] The solidification of the drops of the dispersed phase by heating is suitably carried out at a temperature of 70 to 150 ° C, generally from 80 to 110 ° C, preferably from 90 to 110 ° C.
[148] To isolate the solidified particles, the reaction mixture is allowed to decant and the solidified particles are recovered from this reaction mixture, for example, by siphoning or by a current filtration unit.
[149] The solidified particulate product can be washed at least once up to 6 times, preferably at least twice, more preferably at least three times with a hydrocarbon, which is preferably selected from aromatic and aliphatic hydrocarbons, preferably with toluene, heptane or pentane, more preferably toluene, particularly with hot toluene (for example, from 80 to 100 ° C), which may include a greater or lesser amount of TiCl4 in it. The amount of TiCl4 can vary from a few% by volume to more than 50% by volume, as from 5% by volume to 50% by volume, preferably from 5 to 15% by volume. It is also possible that at least one wash is done with 100% by volume of TiCl4.
[150] One or more additional washes after washes with TiCl4 and / or aromatics can be performed with aliphatic hydrocarbons of 4 to 8 carbon atoms. Preferably, these last two washes are performed with heptane and / or pentane. Washes can be done with hot hydrocarbons (for example, 90 ° C) or cold (room temperature), or combinations of them. It is also possible that all washes are done with the same solvent, for example, toluene.
[151] Washing can be optimized to produce a catalyst component with new and desirable properties.
[152] Finally, the washed catalyst component is recovered.
[153] It can be additionally dried, such as by evaporation or spraying with nitrogen, or it can be fluidized to an oily liquid without any drying step.
[154] In addition, during the preparation of the catalyst component, a reducing agent, which decreases the amount of titanium present in said solidified particles of the olefin polymerization catalyst component being present in the +4 oxidation state, can be added.
[155] Suitable reducing agents are alkyl aluminum compounds, alkyl alkoxy aluminum compounds and magnesium compounds, as defined in this specification.
[156] Suitable aluminum compounds have a general formula AlR3-nXn, where R represents a straight or branched chain alkyl or alkoxy group having from 1 to 20, preferably from 1 to 10 and, more preferably, from 1 to 6 atoms carbon, X independently represents a residue selected from the halogen group, preferably chloride, and n represents 0, 1 or 2. At least one of the R residues must be an alkyl group.
[157] The compound can be added as an optional compound for the synthesis of the catalyst component and placed in contact with the droplets of the dispersed phase of the stirred emulsion before recovering the solidified particles in step (e2). That is, compound A1 can be added at any step (b2) to (d2), or during the washing step as described above, however, before step (e2). Reference is made to WO 2004/029112, EP-A-1862480 and EP-A-1862481.
[158] Illustrative examples of alkyl and alkoxyaluminum compounds to be used according to the present invention are:
[159] Chlorinated trialkyl (C1-C6) -aluminum compounds and aluminum (C1-C6) compounds, especially diethylaluminium chloride; diethyl aluminum ethoxide, ethyl aluminum dioxide, diethyl aluminum methoxide, diethyl aluminum propoxide, diethyl aluminum butoxide, dimethyl aluminum ethoxide, of which, in particular, diethyl aluminum ethoxide is preferred.
[160] Suitable magnesium compounds are magnesium compounds, as defined herein, attached to a group 2 metal complex. The respective disclosure is incorporated into the present invention by reference to the magnesium compound to be added according to process of the present invention. In particular, suitable magnesium compounds are dialkylmagnesium compounds or halogenated alkylmagnesium compounds of the general formula MgR, -nXn, where each n is 0 or 1, and each R is the same or different alkyl groups having 1 to 8 carbon atoms and X is halogen, preferably Cl. A preferred magnesium compound is butyloctylmagnesium (commercially available under the trade name BOMAG), which is already preferentially used in the preparation of the Mg complex.
[161] The amount of optional compound A1 added depends on the desired degree of reduction of the titanium present in solidified particles of the olefin polymerization catalyst component present in the +4 oxidation state. Preferred amounts of Al in the catalyst component depend to some extent on the compound Al, for example, if an alkoxy compound of Al is used, the preferred final amounts of Al appear to be less than if, for example, chloride compounds alkyl aluminum are used.
[162] The particles of the final catalyst component have an Al content of 0.0 to 0.8 wt%, preferably 0.0 to 0.5 wt% or 0.0 to 0.4 wt% .
[163] The magnesium compound to be added according to the present invention is added in corresponding amounts.
[164] Preferably, an Al alkyl or Al alkylalkoxy compound, as defined above, is added.
[165] The aluminum alkyl or alkoxy compound and the magnesium compound can be used alone or in combination.
[166] The optional Al or Mg, or a mixture thereof, is preferably added before step (e2), more preferably during the washing step, which comprises at least one, preferably two and more preferably three hydrocarbon washing procedures the same or, preferably different as the washing medium.
[167] The alkyl or alkoxyaluminum and / or the magnesium compound to be used in the preparation of the catalyst component can be added to any of the washing media, which are, as described above, preferably toluene, heptane and / or pentane.
[168] Although the pro-catalyst preparation according to the method of the invention can be carried out in batches, it is also preferable and possible to prepare the catalyst component semi-continuously or continuously. In such a semi-continuous or continuous process, the solution of the group 2 metal complex and said electron donor, which is prepared by the reaction of said metal compound with said electron donor in an organic liquid reaction medium is mixed with at least a transition metal compound, which can be separated into the same or different organic liquid reaction medium. The solution thus obtained is then stirred, possibly in the presence of an emulsion stabilizer, and then the emulsion thus stirred is fed into a temperature gradient reactor, which the emulsion is subjected to a temperature gradient, thus leading to the solidification of the drops of a dispersed phase of the emulsion. The optional TMA is preferably contained in the solution of the complex or is added to the solution before feeding the stirred solution into the temperature gradient reactor.
[169] When feeding said stirred emulsion into the temperature gradient reactor, an inert solvent, in which the droplets are not soluble, can be additionally fed into that gradient reactor to improve the formation of droplets and, thus, lead to a uniform particle size of the catalyst component particles, which are formed in the temperature gradient reactor when passing through said line. Such an additional solvent can be the same as the organic liquid reaction medium, which is used to prepare the solution of the group 2 metal complex, as explained above, in more detail.
[170] The solidified particles of the olefin polymerization catalyst component can later be recovered by a current filtration unit and then, optionally after a few additional washing and drying steps, to remove the unreacted initial components, they can stored for later use. In one embodiment, the catalyst can be fed after the washing steps in the olefin polymerization reactor, in order to form a continuous preparation and to guarantee the feeding. It is also possible to mix the solidified and washed catalyst component with an oily fluid liquid and store and use the catalyst component as an oily slurry with catalyst component. In this way, drying steps can be avoided, which can sometimes be detrimental to the morphology of the catalyst components. This method of oily slurry is generally described in EP-A-1489110 of the application, incorporated by reference into the present invention.
[171] As can be seen from the above description of the continuous or semi-continuous process, it is thus possible to use separate reaction vessels for the different process steps and transfer the reaction products that are prepared in the respective reaction vessels and feed them in line at other reaction vessels for the formation of the emulsion and, subsequently, of the solidified particles.
[172] It is preferable to use a completely continuous process, as the time savings in said process is remarkable. In such a totally continuous process, the formation of the solidified particles could be carried out in the pipeline reactor temperature gradient line, which is long enough and which is subjected to said temperature gradient from the initial temperature in the lower range of 20 to 80 ° C to a "solidification" temperature of 70 to 150 ° C. The temperature gradient is preferably obtained by heating the pipe reactor outside through the application of normal heaters, microwaves, etc.
[173] As mentioned above, a filter unit can preferably be used to filter the solidified particles from the solvent stream. For said filtration unit, several drums and screening systems can be used, depending on the specific particle sizes.
[174] With both forms of production, the solid catalyst component finally obtained is, desirably, in the form of particles, generally having a range of medium size, determined by the use of a Coulter LS200 counter at room temperature (20 ° C ), with n-heptane as a medium, from 2 to 500 μm, preferably from 5 to 200 μm and, more preferably, from 10 to 100, even an average size range of 20 to 60 μm is possible.
[175] The particle size distribution, measured by the Coulter method and defined as SPAN of the catalysts of the invention depends on the form of preparation. With the emulsion / solidification method, the particle size distribution is generally smaller than with the precipitation method. However, it is desirable that the particle size distribution of the solid catalyst components prepared according to the precipitation method is as low as possible and, even more preferably, similar to that of the solid catalyst components prepared according to the emulsion method. /solidification.
[176] Preferably, the particle size distribution is in the range of 0.5 to a maximum of 4.0, more preferably of 0.5 to a maximum of 3.0 and, even more preferably, of 0.5 to a maximum 2.0.
[177] SPAN is defined as
where d90 indicates the particle diameter at 90% cumulative size, d10 indicates the particle diameter at 10% cumulative size and d50 indicates the particle diameter at 50% cumulative size.
[178] The catalyst components prepared according to the method of the present invention have the desired particle size and morphology, as well as the particle size distribution and produce catalysts with enhanced catalyst activity, which are suitable for producing polymers with the following characteristics: polymer properties desired.
[179] It has been surprisingly found by the inventors of the present invention that the catalyst component particles that have the desired particle size and morphology, as well as the desired particle size distribution can be obtained by a common mechanism through the precipitation preparation pathway. or emulsion / solidification of Ziegler-Natta (Zn) type catalysts, and are suitable for use in the polymerization of olefins, such as ethylene or propylene, in particular for the polymerization of propylene, optionally with other comonomers selected from C2-C12 monomers, preferably C2 monomers -C6.
[180] The method of the present invention provides even more possibilities for changing the donor type and adjusting the donor concentrations, which allows the preparation of catalysts and other polymers with the desired properties.
[181] Thus, it is another object of the present invention to provide catalyst components, in the form of solid particles, through a process as described above and to use them for the preparation of a suitable catalyst system for polymerization processes. of olefin.
[182] Polymerization processes, where the catalyst components of the invention are useful, comprise at least one polymerization stage, where polymerization is usually carried out in solution phase, slurry, bulk or gas. Typically, the polymerization process comprises polymerization stages or additional reactors. In a particular embodiment, the process contains at least one bulk reactor zone and at least one gas phase reactor zone, each zone comprising at least one reactor, and all reactors being cascaded. In a particularly preferred embodiment, the polymerization process for polymerizing olefins, particularly propylene, optionally with comonomers, such as ethylene or other alpha-olefins, comprises at least one mass reactor and at least one gas phase reactor arranged in that order. In some preferred processes, the process comprises a mass reactor and at least two, for example, two or three gas phase reactors. The process can also comprise pre- and post-reactors. Pre-reactors typically comprise prepolymerization reactors. In these types of processes, the use of a higher polymerization temperature (70 ° C or higher, preferably 80 ° C or higher, even 85 ° C or higher) in some or all of the reactors in the reactor cascade, is preferred to achieve some specific properties for polymers.
[183] For the production of polypropylene homo or copolymers according to the invention, the catalyst system used comprises, in addition to the catalyst components in the form of solid particles, as described above, an organometallic cocatalyst.
[184] Therefore, it is preferable to select the cocatalyst from the group consisting of trialkylaluminium, such as triethylaluminium (TEA), triisobutylalumin, tri-n-butylalumin; dialkyl aluminum chloride, such as dimethyl or diethyl aluminum chloride; and aluminum alkyl sesquichloride. More preferably, the cocatalyst is triethyl aluminum or diethyl aluminum chloride, more preferably triethyl aluminum is used as a cocatalyst.
[185] Optionally, one or more external donors are used, which can typically be selected, for example, from silanes or any other external donors well known in the field. External donors are known in the art and are used as stereoregulating agents in the polymerization of propylene. External donors are preferably selected from hydrocarbiloxysilane compounds, aminosilanes and hydrocarbiloxyalane compounds.
[186] Typical hydrocarbiloxysilane compounds have the formula (VII) R7pSi (OR8) 4-p (VII) where R7 is an alpha or beta-branched C3-C12 hydrocarbyl, R8 is a C1-C12 hydrocarbyl, and p is an integer of 1 to 3.
[187] More specific examples of compostoshidrocarbiloxissilanos, which are useful as external electron donors in the invention are difenildimetoxissilano, dicyclopentyldimethoxysilane, diciclopentildietoxissilano, ciclopentilmetildimetoxissilano, ciclopentilmetildietoxissilano, hexildimetoxissilano dicyclohexylcarbodiimide, dicyclohexylcarbodiimide hexildietoxissilano, hexilmetildimetoxissilano cyclohexane, cyclohexane hexilmetildietoxissilano, metilfenildimetoxissilano, difenildietoxissilano , cyclopentyltrimethoxysilane, phenyltrimethoxysilane, cyclopentyltriethoxysilane and phenyltriethoxysilane.
[188] More preferably, the alkoxysilane compound of formula (VII) is dicyclopentyldimethoxysilane or cyclohexylmethyldimethoxysilane.
[189] Typical aminosilane compounds have the formula (VIII) Si (OR9) 3 (NR10R11) where
[190] R9 is a hydrocarbon group with 1 to 6 carbon atoms, R10 is a hydrocarbon group with 1 to 12 carbon atoms or hydrogen atom, and R11 is a hydrocarbon group with 1 to 12 carbon atoms.
[191] Preferably, these compounds have the formula (IX) Si (OCH2CH3) 3 (NR10R11) in which
[192] R10 and R11 are independently selected from the group consisting of linear aliphatic hydrocarbon group with 1 to 12 carbon atoms, branched aliphatic hydrocarbon group, with 1 to 12 carbon atoms and cyclic aliphatic hydrocarbon group, with 1 to 12 carbon atoms.
[193] It is particularly preferred that R10 and R11 are independently selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, octyl, decanyl, isopropyl, isobutyl, isopentyl, tert-butyl, tert-amyl, neopentyl, cyclopentyl , cyclohexyl, methylcyclopentyl and cycloheptyl.
[194] More preferably, R10 and R11 are the same and have 1 to 6 carbon atoms, even more preferably R10 and R11 are a C1-C4 alkyl group.
[195] More preferably, the external donor represented by the formula (VIII) or (IX) is diethylaminotrietoxysilane.
[196] The external donor used for the catalyst system is therefore preferably diethylaminotrietoxysilane, dicyclopentyldimethoxysilane or cyclohexylmethyldimethoxysilane.PART EXPERIMENTAL1. METHODS
[197] Flow rate of MFR cast material: ISO 1133; 230 ° C 2.16 kg load
[198] PSD particle size distribution:
[199] Coulter LS 200 counter at room temperature with heptane as the medium
[200] The average particle size is reported in μm and measured with the Coulter LS200 counter at room temperature with n-heptane as a medium; particle sizes below 100 nm, by transmission electron microscopy.
[201] The median particle size (d50) is given in μm and is measured with the Coulter LS200 counter at room temperature with n-heptane as a medium.
[202] The particle size (d10) is given in μm and is measured with the Coulter LS200 counter at room temperature with n-heptane as a medium.
[203] The particle size (d90) is given in μm and is measured with the Coulter LS200 counter at room temperature with n-heptane as a medium.
[204] SPAN is defined as follows:

[205] Analysis of ICP (Al, Mg, Ti)
[206] Elemental analysis of a catalyst was carried out by taking a solid sample from the mass, M and cooling it on dry ice. The samples were diluted to a known volume, V, dissolving in nitric acid (HNO3, 65%, 5% V) and freshly deionized water (DI) (5% V). The solution was further diluted with water DI until the final volume, V, and allowed to stabilize for two hours. The analysis was performed at room temperature using an optical emission spectrometer with inductively coupled plasma (ICP-OES) Thermo Elemental iCAP 6300 that was calibrated using a blank (5% HNO3 solution) and 0.5 ppm standards, 1 ppm, 10 ppm, 50 ppm, 100 ppm and 300 ppm of Al, Mg and Ti in 5% HNO3 solutions.
[207] Immediately before analysis the calibration is "re-tilted" using the standard 100 ppm blank, a quality control sample (20 ppm Al, Mg and Ti in a 5% HNO3 solution, 3% HF in DI water) is analyzed to confirm the reclination. The QC sample is also analyzed after every 5th sample and at the end of a set of scheduled analyzes.
[208] The Mg content was monitored using the 285,213 nm line and the Ti content using the 336,121 nm line. The aluminum content was monitored through the 167,079 nm line, when the Al concentration in the ICP sample was between 0 and 10 ppm (calibrated only up to 100 ppm) and through the 396,152 nm line for Al concentrations above 10 ppm .
[209] The reported values are an average of three successive aliquots taken from the same sample and are correlated to the original catalyst by introducing the original sample mass and dilution volume into the software. Determination of donor quantities in the catalyst components
[210] The determination of donor quantities in the catalyst components is carried out using HPLC (UV detector, column RP-8, 250 mm x 4 mm). Pure donor compounds are used to prepare standard solutions.
[211] 50 to 100 mg of the catalyst component are weighed in a 20 ml flask (0.1 mg weighing accuracy). 10 ml of acetonitrile are added and the sample suspension is subjected to ultrasound for 5 to 10 min in an ultrasound bath. The acetonitrile suspension is adequately diluted and a liquid sample is filtered using a 0.45 μm filter for the HPLC instrument sample vial. Peak heights are obtained by HPLC.
[212] The percentage of donor in the catalyst component is calculated using the following equation: Percentage (%) = A1 xcx V x A2-1 x m-1 x 0.1% whereA1 = peak height of the sample = concentration of the standard solution (mg / L) V = volume of the sample solution (mL) A2 = peak height of the standard = sample weight (mg) Donor analysis by GC
[213] The donor analysis of a catalyst was performed by removing a solid sample from the mass, M, about 2 mL of solvent, dichloromethane, was added. After that, about 1 mL of deionized water was added to the flask. Finally, a known mass, N, of a standard, nonane intern, was added. The mixture was then subjected to ultrasound for 15 min to ensure complete dissolution.
[214] After ultrasound, the sample is left to stand in two phases and an aliquot of the organic phase is removed, which is then filtered through a 0.45 μm nylon filter in a flask suitable for the instrument. gas chromatography.
[215] The analysis is performed on a Perkin Elmer Auto System XL gas chromatograph containing a split loop injector and a flame ionization detector. The column is a DB-1 30 m long with an internal diameter of 0.32 mm and a phase thickness of 0.25 μm. The system is at 40 ° C for 5 minutes before increasing the temperature to 10 ° C / min until it reaches 250 ° C; the system is kept at that temperature for another 4 minutes. If necessary, the maximum temperature could be increased up to 300 ° C. The results are calculated as follows: Component (% by weight) = Where: Ax = component area F = component factorN = mass of the internal standard (nonane), mgAy = area of the internal standard (nonane) Fistd = factor of the internal standard (nonane) M = mass of the sample, mg Randomness
[216] Infrared (IR) spectroscopy was performed on a Nicolet Magna IR 550 spectrometer. A 220 to 250 μm film was prepared from the polymeric powder at 230 ° C, followed by rapid cooling to room temperature. All IV analyzes were performed within two hours of film preparation.
[217] Quantitative comonomer contents were obtained using peak areas normalized to the peak height of an internal reference band calibrated for previous 13C NMR results. Ethylene was quantified using the band at 733 cm-1 (baseline from 690 to 780 cm-1) and the reference band at 809 cm-1 (baseline from 750 to 890 cm-1). The number of isolated ethylene units (randomness) was estimated using the peak height of the band at 733 cm-1 (baseline 690 to 780 cm-1) and the same reference band described above. Calibration was done for the previously obtained 13C NMR results.
[218] Randomness = random ethylene content (-P-E- P -) / total ethylene content x 100%. Material soluble in xylene XS: fraction soluble in xylene of the product at 25 ° C.
[219] 2.0 g of polymer are dissolved in 250 ml of p-xylene at 135 ° C, with stirring. After 30 ± 2 minutes, the solution is allowed to cool for 15 minutes at room temperature and then allowed to decant for 30 minutes at 25 ± 0.5 ° C. The solution is filtered with filter paper in two 100 ml flasks.
[220] The solution of the first 100 mL container is evaporated in a nitrogen flow and the residue is dried under vacuum at 90 ° C until it reaches a constant weight.XS% = (100 x mL x v0) / (m0 x v1) m0 = quantity of initial polymer (g) m1 = weight of the residue (g) V0 = initial volume (mL) v1 = volume of the sample analyzed (mL) All reactions in the examples as described are carried out under inert conditions.EXAMPLESExample 1: Preparation of Mg alkoxide
[221] 43.9 mL of 2-ethylhexanol was added to a 300 mL glass reactor. 123.9 ml of a 20% solution of BOMAG (butyloctylmagnesium), supplied by Crompton GmbH, was slowly added to the well-mixed 2-ethylhexanol. During the addition, the temperature was kept below 40 ° C. Then, the temperature of the reaction mixture was raised to 60 ° C and the mixture continued at this temperature for 60 minutes. Finally, the Mg alkoxide was transferred to vials with septa after cooling to room temperature. Example 2: Donor in situ preparation
[222] 5.05 mL (5.25 g) of 1,2-propylene glycol were added to a 300 mL glass reactor at room temperature. 61.9 ml of a 20% toluene solution of BOMAG provided by Crompton GmbH was slowly added to the well mixed propylene glycol. During the addition, the temperature was kept below 40 ° C. Then, the temperature of the reaction mixture was raised to 60 ° C and the mixture continued at this temperature for 60 minutes. After cooling the reaction mixture to room temperature, 17.80 g of benzoyl chloride was added. The temperature of the reaction mixture was raised to 60 ° C and the mixing at that temperature continued for an additional hour. Finally, the donor suspension thus obtained was transferred to vials with septa after cooling to room temperature. Example 3: Preparation of the Mg complex
[223] 9.60 mL (8.45 g) of the Mg alkoxide prepared according to example 1 were placed in a flask with a septum (N2 atmosphere, equipped with a magnetic stir bar). 6.40 ml (5.63 g) of the donor suspension prepared according to example 2 was added at room temperature and the reaction mixture was mixed for 1 hour at room temperature. Example 4: (Comparative Example CE1) Preparation of the catalyst component
[224] 6.5 mL of titanium tetrachloride were placed in a 300 mL reactor equipped with a mechanical stirrer at 25 ° C. The mixing speed was adjusted to 400 rpm. 4.2mL of a mixture consisting of 0.30 ml of a 0.60 mg ethanol solution of Necadd 447, 0.6 ml of a 50% by weight solution in toluene of Viscoplex 1-254 and 3.30 ml of heptane were added at the same time. Then, the reactor temperature rose to 90 ° C in 5 minutes. When the temperature is reached, 11.0 ml of the Mg complex prepared according to example 3 were added within 15 minutes at a constant feed rate, whereby the temperature was maintained at 90 ° C during the addition. The reaction mixture was stirred for an additional 30 minutes at 90 ° C. After that, stirring was stopped and the reaction mixture was allowed to settle for 15 minutes at 90 ° C.
[225] After standing and siphoning, the solids were subjected to 3 washing steps: Wash 1: wash with and toluene / DEAC
[226] Wash with a mixture of 0.03 ml of diethyl aluminum chloride and 33 ml of toluene at 90 ° C for 30 minutes under stirring at 300 rpm. After that, stirring was stopped and the reaction mixture was left to stand for 15 minutes at 90 ° C, with subsequent siphoning. Wash 2: 1st wash with heptane
[227] Wash with 20 ml of heptane at 90 ° C for 7 minutes under agitation at 300 rpm.
[228] After that, the reaction temperature decreases to 25 ° C for 13 minutes. Then, the stirring was stopped and the reaction mixture was left to stand for 15 minutes at 25 ° C, with subsequent siphoning. Wash 3: 2nd wash with heptane
[229] Wash with 20 ml of heptane at 25 ° C for 20 minutes under agitation at 300 rpm.
[230] Thereafter, stirring was stopped and the reaction mixture was left to stand for 10 minutes at 25 ° C, with subsequent siphoning.
[231] Finally, the temperature was raised to 70 ° C for 7 minutes, followed by spraying N2 for 20 minutes to produce an air-sensitive powder. Example 5: Preparation of Mg alkoxide
[232] 41.4 mL of propylene glycol butyl ether were added to a 300 mL glass reactor. 123.9 ml of a 20% toluene solution of BOMAG, supplied by Crompton GmbH, was slowly added to the well mixed etherpropylene glycol ether. During the addition, the temperature was kept below 40 ° C. Then, the temperature of the reaction mixture was raised to 60 ° C and the mixture continued at this temperature for 60 minutes. Finally, the Mg alkoxide was transferred to vials with septa after cooling to room temperature. Example 6: Preparation of the Mg complex
[233] 6.27 mL (5.52 g) of the Mg alkoxide prepared according to example 1 were placed in a septum flask (N2 atmosphere, equipped with a magnetic stir bar). 4.18 ml (3.68 g) of the donor suspension prepared according to Example 2 was added at room temperature. Then 5.17 ml (4.60 g) of the Mg alkoxide prepared according to example 5 were added at room temperature and the reaction mixture was mixed for 1 hour at room temperature. Example 7: Preparation of the catalyst component
[234] 6.5 mL of titanium tetrachloride was placed in a 50 mL glass reactor equipped with a mechanical stirrer at 25 ° C. The mixing speed was adjusted to 400 rpm. 4.2 ml of a mixture consisting of 0.30 ml of a solution in toluene of 0.60 mg of Necadd 447, 0.6 ml of a solution of 50% by weight in toluene of Viscoplex 1-254 and 3.30 ml of heptane were added at the same time. Then, the reactor temperature rose to 90 ° C in 5 minutes. When the temperature is reached, 11.0 ml of the Mg complex prepared according to example 6 were added within 15 minutes at a constant feed rate, whereby the temperature was maintained at 90 ° C during the addition. The reaction mixture was stirred for an additional 30 minutes at 90 ° C. After that, stirring was stopped and the reaction mixture was allowed to settle for 15 minutes at 90 ° C.
[235] After standing and siphoning, the solids were subjected to 3 washing steps: Wash 1: wash with and toluene / DEAC
[236] Wash with a mixture of 0.03 ml of dediethyl aluminum chloride and 33 ml of toluene at 90 ° C for 30 minutes under stirring at 300 rpm. After that, stirring was stopped and the reaction mixture was left to stand for 15 minutes at 90 ° C, with subsequent siphoning. Wash 2: 1st wash with heptane
[237] Wash with 20 ml of heptane at 90 ° C for 7 minutes under agitation at 300 rpm.
[238] After that, the reaction temperature decreases to 25 ° C for 13 minutes. Then, the stirring was stopped and the reaction mixture was left to stand for 15 minutes at 25 ° C, with subsequent siphoning. Wash 3: 2nd wash with heptane
[239] Wash with 20 ml of heptane at 25 ° C for 20 minutes under agitation at 300 rpm.
[240] Thereafter, stirring was stopped and the reaction mixture was left to stand for 10 minutes at 25 ° C, with subsequent siphoning.
[241] Finally, the temperature was raised to 70 ° C for 7 minutes, followed by spraying N2 for 20 minutes to produce an air-sensitive powder. Example 8: In situ preparation of the donor
[242] 5.0 mL (5.25 g) of 1,3-propylene glycol were added to a 300 mL glass reactor at room temperature. 61.9 mL of a 20% toluene solution of BOMAG (Mg (Bu) 1.5 (Oct) 0.5) supplied by Crompton GmbH was slowly added to the well-mixed propylene glycol.
[243] During the addition, the temperature was kept below 40 ° C. Then, the temperature of the reaction mixture was raised to 60 ° C and the mixture continued at this temperature for 60 minutes. After cooling the reaction mixture to room temperature, 17.80 g of benzoyl chloride was added. The temperature of the reaction mixture was raised to 60 ° C and the mixing at that temperature continued for an additional hour. Finally, the donor suspension thus obtained was transferred to vials with septa after cooling to room temperature. Example 9 Preparation of the Mg complex
[244] 9.60 mL (8.45 g) of the Mg alkoxide prepared according to example 1 were placed in a septum flask (N2 atmosphere, equipped with a magnetic stir bar). 6.40 mL (5.63 g) of the donor suspension prepared according to example 8 was added at room temperature and the reaction mixture was mixed for 1 hour at room temperature. Example 10: (Comparative example CE2) Preparation of the catalyst component
[245] The catalyst component was prepared as described in example 7, except that the Mg complex prepared according to example 9 was used. Example 11: Preparation of the Mg complex
[246] 6.27 mL (5.52 g) of the Mg alkoxide prepared according to example 1 were placed in a septum flask (N2 atmosphere, equipped with a magnetic stir bar). 4.18 ml (3.68 g) of the donor suspension prepared according to Example 8 was added at room temperature. Then 5.17 ml (4.60 g) of the Mg alkoxide prepared according to example 5 were added at room temperature and the reaction mixture was mixed for 1 hour at room temperature. Example 12: Preparation of the catalyst component
[247] The catalyst component was prepared as described in example 7, except that the Mg complex prepared according to example 11 was used. Example 13: Preparation of the Mg complex
[248] 30.0 mL (26.4 g) of the Mg alkoxide prepared according to example 1 were placed in a septum flask (N2 atmosphere, equipped with a magnetic stir bar). 2.24 g of diethyl-2-cyclopentyl maleate was added slowly at room temperature and the reaction mixture was mixed for 10 minutes at room temperature. Example 14: (Comparative Example CE3) Preparation of the catalyst component
[249] The catalyst component was prepared as described in example 7, except that the Mg complex prepared according to example 13 was used. Example 15: Preparation of the Mg complex
[250] 10.04 mL (8.87 g) of the Mg alkoxide prepared according to example 1 were placed in a flask with a septum (N2 atmosphere, equipped with a magnetic stir bar). 4.96 ml (4.33 g) of the Mg alkoxide prepared according to example 5 were added at room temperature. Then, 1.13 g of diethyl-2-cyclopentyl maleate was added at room temperature and the reaction mixture was mixed for 1 hour at room temperature. Example 16: Preparation of the catalyst component
[251] The catalyst component was prepared as described in example 7, except that the Mg complex prepared according to example 15 was used. Example 17: Preparation of the Mg complex
[252] 15.0 mL (13.20 g) of the Mg alkoxide prepared according to example 1 were placed in a septum flask (N2 atmosphere, equipped with a magnetic stir bar). Then, 1.19 g of diethyl-2-cyclohexyl maleate was added at room temperature and the reaction mixture was mixed for 10 minutes at room temperature. Example 18: (Comparative Example CE4) Preparation of the catalyst component
[253] The catalyst component was prepared as described in example 7, except that the Mg complex prepared according to example 17 was used. Example 19: Preparation of the Mg complex
[254] 10.04 ml (8.87 g) of the Mg alkoxide prepared according to example 1 were placed in a septum flask (N2 atmosphere, equipped with a magnetic stir bar). 4.96 ml (4.33 g) of the Mg alkoxide prepared according to example 5 were added at room temperature. Then, 1.19 g of diethyl-2-cyclohexyl maleate was added at room temperature and the reaction mixture was mixed for 10 minutes at room temperature. Example 20: Preparation of the catalyst component
[255] The catalyst component was prepared as described in example 7, except that the Mg complex prepared according to example 19 was used. Example 21: Preparation of the Mg complex
[256] 15.0 mL (13.20 g) of the Mg alkoxide prepared according to example 1 were placed in a flask with a septum (N2 atmosphere, equipped with a magnetic stir bar). Then, 1.07 g of diethyl-2-isobutyl maleate was added at room temperature and the reaction mixture was mixed for 10 minutes at room temperature. Example 22: (Comparative Example CE5) Preparation of the catalyst component
[257] The catalyst component was prepared as described in example 7, except that the Mg complex prepared according to example 21 was used. Example 23: Preparation of the Mg complex
[258] 10.04 mL (8.87 g) of the Mg alkoxide prepared according to example 1 were placed in a septum flask (N2 atmosphere, equipped with a magnetic stir bar). 4.96 ml (4.33 g) of the Mg alkoxide prepared according to example 5 was added at room temperature. Then, 1.07 g of diethyl-2-isobutyl maleate was added at room temperature and the reaction mixture was mixed for 10 minutes at room temperature. Example 24: Preparation of the catalyst component
[259] The catalyst component was prepared as described in example 7, except that the Mg complex prepared according to example 23 was used. Example 25: Preparation of the Mg complex
[260] 11.2 ml (9.84 g) of the Mg alkoxide prepared according to example 1 were placed in a flask with a septum (N2 atmosphere, equipped with a magnetic stir bar). 2.80 ml (2.46 g) of the Mg alkoxide prepared according to example 5 were added at room temperature. Then, 1.00 g of diethyl-2-isobutyl maleate was added slowly at room temperature and the reaction mixture was mixed for 5 minutes at room temperature. Example 26: Preparation of the catalyst component
[261] The catalyst component was prepared as described in example 7, except that the Mg complex prepared according to example 25 was used. Example 27: Preparation of Mg alkoxide
[262] 16.0 mL of propylene glycolethyl ether were added to a 300 mL glass reactor. 63.0 ml of a 20% toluene solution of BOMAG, supplied by Crompton GmbH, was slowly added to the well mixed etherpropylene glycol. During the addition, the temperature was kept below 40 ° C. Then, the temperature of the reaction mixture was raised to 60 ° C and the mixture continued at this temperature for 60 minutes. Finally, the Mg alkoxide was transferred to vials with septa after cooling to room temperature. Example 28: Preparation of the Mg complex
[263] 8.30 mL (7.30 g) of the Mg alkoxide prepared according to example 1 were placed in a septum flask (N2 atmosphere, equipped with a magnetic stir bar). 4.17 ml (3.66 g) of the Mg alkoxide prepared according to example 27 were added at room temperature. Then, 0.89 g of diethyl-2-isobutyl maleate was added slowly at room temperature and the reaction mixture was mixed for 5 minutes at room temperature. Example 29: Preparation of the catalyst component
[264] The catalyst component was prepared as described in example 7, except that the Mg complex prepared according to example 28 was used. Example 30: Preparation of the Mg complex
[265] 11.2 mL (9.84 g) of the Mg alkoxide prepared according to example 1 were placed in a septum flask (N2 atmosphere, equipped with a magnetic stir bar). 2.80 ml (2.46 g) of the Mg alkoxide prepared according to example 27 was added at room temperature. Then, 1.00 g of diethyl-2-isobutyl maleate was added slowly at room temperature and the reaction mixture was mixed for 5 minutes at room temperature. Example 31: Preparation of the catalyst component
[266] The catalyst component was prepared as described in example 7, except that the Mg complex prepared according to example 30 was used.Table 1: Composition of the catalyst components

1) maximum donor amount calculated according to the formula: 100 - (3,917 * Mg% + 4,941 * Al% + 3,962 * Ti%) = maximum donor amount (%) based on the assumption that all Mg is in the form of MgCl2, all Al is in the form of AlCl3 and all Ti is in the form of TiCl4, and no hydrocarbons are present. Example 32: PP polymerization procedure on a bench scale
[267] A 5 liter stainless steel reactor was used to polymerize e propylene.
[268] About 0.9 mL of triethyl aluminum (TEA) (obtained from Witco, used as received) as a cocatalyst, ca. 0.13 ml of dicyclopentyldimethoxysilane (DCDS) (obtained from Wacker, dried with molecular sieves) as an external donor and 30 ml of n-pentane were mixed and allowed to react for 5 minutes. Half of the mixture was then added to the polymerization reactor and the other half was mixed with about 20 mg of a catalyst. After an additional 5 minutes, the catalyst / TEA / donor / n-pentane mixture was added to the reactor. The Al / Ti ratio was equal to 250 mol / mol and the Al / DCDS ratio was equal to 10 mol / mol. 200 mmol of hydrogen and 1400 g of propylene were introduced into the reactor and the temperature was raised within about 15 minutes to the polymerization temperature (80 ° C). The polymerization time after reaching the polymerization temperature was 60 minutes, after which the polymer formed was removed from the reactor.Table 2: Results of the polymerization


[269] As can be seen in Table 2, the catalyst components produced with the special alcohol mixture show significantly higher activities than those prepared according to the state of the art using only monohydric alcohols.

权利要求:
Claims (25)
[0001]
1. Process for preparing an olefin polymerization catalyst component in the form of solid particles, CHARACTERIZED by comprising the steps of (a1) (a1-1) providing a solution (S1) of a first alkoxy compound (Ax) being the product of the reaction of a metal compound from group 2 and an alcohol mixture of a monohydric alcohol (A) of the formula ROH, with R being C6-C10 alkyl and an alcohol (B) selected from ethylene glycol butyl ether, ethylene glycol hexyl ether, ethylene glycol 2-ethylhexyl ether, propylene glycol n-butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-hexyl ether and propylene glycol 2-ethylhexyl ether; or (a1-2) providing a solution (S1) of a mixture of an alkoxy compound (Ax) being the product of a group 2 metallic compound and a monohydric alcohol (A) of the formula ROH, with R being C6-C10 alkyl, and a second alkoxy compound (Bx) being the product of the reaction of a compound group 2 and an alcohol (B) selected ionized from ethylene glycol butyl ether, ethylene glycol hexyl ether, ethylene glycol2-ethylhexyl ether, propylene glycol n-butyl ether, propylene glycolmethyl ether, propylene glycol ethyl ether, propylene glycol n-hexyl ether and an internal propylene glycol and propylene glycol ether; themselves, or a corresponding precursor thereof in an organic reaction medium (OM1), (b1) combining said solution (S1) with a transition metal compound (CT), and (c1) precipitating said catalyst component in the form of a solid particle, and (d1) recovering the solidified particles from the olefin polymerization catalyst component in which the internal donors are selected from i) benzoates of the formula (I)
[0002]
2. Process according to claim 1, CHARACTERIZED by the fact that step (a1) is carried out in a liquid organic reaction medium.
[0003]
3. Process according to claim 1 or 2, CHARACTERIZED by the fact that in the benzoates of formula (I) internal dodo (i), R 'being a ouramified linear C1-C12-alkyl group, the alkyl group contains a heteroatom selected from O, N or S in the alkyl chain.
[0004]
4. Process according to any one of claims 1 to 3, CHARACTERIZED by the fact that in the benzoates of formula (I) of the internal donor (i), R 'being a linear ouramified C1-C12 alkyl group, the alkyl group is replaced by = O, halogen or substituted or unsubstituted C6-C14-aryl.
[0005]
5. Process according to any one of claims 1a 4, CHARACTERIZED by the fact that in the 1,3-diethers of formula (V) or (VI) of the internal donor (iv), R3 and R4 together forming a ring with 5 to 10 carbon atoms, said ring is part of an aliphatic or aromatic polycyclic ring system with 9 to 20 carbon atoms.
[0006]
6. Process according to any one of claims 1 to 5, CHARACTERIZED by the fact that the addition of the solution (S1) to a transition metal compound (CT) in step (b1) is carried out in a temperature range of 50 to 110 ° C, temperature at which a transition metal (CT) compound is in a liquid form, resulting in the precipitation of the solid catalyst components.
[0007]
7. Process, according to claim 6, CHARACTERIZED by the fact that a surfactant is added in step (a1) or step (b1).
[0008]
8. Process according to any one of claims 1 to 7, CHARACTERIZED by the fact that the solution (S1) is mixed with a transition metal compound (CT), in liquid form at a temperature of -20 ° C to 30 ° C , and the precipitation of the solid catalyst components occurs by the subsequent slow rise in temperature to a temperature range of 50 to 110 ° C, through which the rate of temperature rise is in the range of 0.1 ° C to 30 ° C per minute, whereby an activator is added to the solution (S1) before step (b1).
[0009]
9. Process according to claim 8, CHARACTERIZED by the fact that the rate of temperature increase is in the range of 0.5 ° C to 10 ° C per minute.
[0010]
10. Process for preparing an olefin polymerization catalyst component in the form of solid particles, CHARACTERIZED by the fact that it comprises the steps of (a2) (a2-1) providing a solution (S1) of a first alkoxy compound (Ax) being the product of the reaction of a group 2 metallic compound and an alcohol mixture of a monohydric alcohol (A) of the formula ROH, with R being C6-C10 alkyl and an alcohol (B) selected from ethylene glycol butyl ether, ethylene glycol hexyl ether, ethylene glycol 2-ethylhexyl ether, propylene glycol n-butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-hexyl ether and propylene glycol 2-ethylhexyl ether; or (a2-2) providing a solution (S1) of a mixture of an alkoxy compound first alkoxy compound (Ax) being the product of a group 2 metal compound and a monohydric alcohol (A) of the formula ROH, with R being C6-C10 alkyl, and a second alkoxy compound (Bx) being the reaction product of a group 2 compound and an alcohol cool (B) selected from ethylene glycol butyl ether, ethylene glycol hexyl ether, ethylene glycol2-ethylhexyl ether, propylene glycol n-butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether and propylene glycol n-hexylene ether and internal propylene glycol and propylene glycol ether; or a mixture thereof, or a precursor thereof, in an organic liquid reaction medium, (b2) add said solution (S1) to a transition metal compound to produce an emulsion, the dispersed phase being in the form of drops and contains more than 50 mol% of the metal of group 2, (c2) stir the emulsion to keep the drops of said phased dispersion in said range of predetermined average size from 2 to 500µm, (d2) solidify said drops of the dispersed phase, (e2) recovering the solidified particles of the olefin polymerization catalyst component in which the internal donors are selected from i) benzoates of formula (I)
[0011]
11. Process, according to claim 10, CHARACTERIZED by the fact that step (a1) is carried out in an organic liquid reaction medium.
[0012]
12. Process according to claim 10 or 11, CHARACTERIZED by the fact that in the benzoates of formula (I) of the internal donor (i), R 'being a linear or branched C1-C12-alkyl group, the alkyl group contains a heteroatom selected from O, N or S in the alkyl chain.
[0013]
13. Process according to any one of claims 10 to 12, CHARACTERIZED by the fact that in the benzoates of formula (I) of the internal donor (i), R 'being a straight or branched C 1 -C 2 alkyl group, the group alkyl is replaced by = O, halogen or substituted or unsubstituted C6-C1-4 aryl.
[0014]
14. Process according to any one of claims i0 to i3, CHARACTERIZED by the fact that in the i, 3-diethers of the formula (V) or (VI) of the internal donor (iv), R3 and R4 together forming a ring with 5 to 10 carbon atoms, said ring is part of an aliphatic or aromatic polycyclic ring system with 9 to 20 carbon atoms.
[0015]
15. Process, according to any of claims i to i4, CHARACTERIZED by the fact that it is performed continuously.
[0016]
16. Process according to any one of claims ia i5, CHARACTERIZED by the fact that in step (ai) or (a2) a solution of a mixture of alkoxy compound according to ai) is used in which the alcohols (A) and (B) are employed at a molar ratio of 6: iai: 6.
[0017]
17. Process according to any one of claims i to i6, CHARACTERIZED by the fact that said Group 2 metal is magnesium.
[0018]
18. Process according to any one of claims 1 to 17, CHARACTERIZED by the fact that said metal is Group 4 and / or Group 5 metal.
[0019]
19. Process, according to claim 18, CHARACTERIZED by the fact that said transition metal is Ti.
[0020]
20. Particles of the catalyst component, CHARACTERIZED in that they can be obtained as defined in any one of claims 1 to 14.
[0021]
21. Olefin polymerization catalyst, CHARACTERIZED by the fact that it comprises particles of the catalyst component, as defined in claim 20 and a cocatalyst.
[0022]
22. Olefin polymerization catalyst, according to claim 21, CHARACTERIZED by the fact that it comprises an external electron donor.
[0023]
23. Olefin polymerization catalyst according to claim 21 or 22, CHARACTERIZED by the fact that the cocatalyst is an alkyl aluminum cocatalyst.
[0024]
24. Use of the catalyst as defined in any of claims 21 to 23, CHARACTERIZED by the fact that it is for olefin polymerization.
[0025]
25. Use, according to claim 24, CHARACTERIZED by the fact that said polymerization is with C2 to C12 monomers.

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同族专利:

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公开号 | 公开日

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BR112014015791A8|2017-07-04|

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BR112014015791A2|2017-06-13|

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JP2015503647A|2015-02-02|

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EP2610271B1|2019-03-20|

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-09-29| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

---

2021-01-26| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-03-16| B09X| Republication of the decision to grant [chapter 9.1.3 patent gazette]|

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2021-03-30| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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