catalyst composition for the polymerization of olefins, its process for the preparation and use, cat

专利摘要:
CATALYST COMPOSITION FOR THE POLYMERIZATION OF OLEFINS. The present invention relates to a catalyst composition comprising a monoester, the compound represented by formula (I) as an internal electron donor, and optionally an additional internal electron donor selected from the group consisting of diesters and diethers, OCOR8 R3 R4 R3 R2 R5 R6 NR7COR8 Formula (I) where: R1, R2, R3, R4, R5 and R6 are the same or different and are independently selected from the group consisting of hydrogen, straight, branched and cyclic alkyl having a maximum of 20 carbon atoms and aromatic substituted or unsubstituted hydrocarbyl having 6 to 20 carbon atoms; R7 is selected from the group consisting of straight, branched and cyclic alkyl having a maximum of 20 carbon atoms and aromatic substituted or unsubstituted hydrocarbyl having from 6 to 20 carbon atoms; and R8 is selected from the group consisting of aromatic substituted or unsubstituted hydrocarbyl having 6 to 20 carbon atoms. The present invention also relates to a process for preparing said catalyst polymerization composition and to a polymerization catalyst system comprising said catalyst composition, a co-catalyst and optionally (...).
公开号:BR112015017749B1
申请号:R112015017749-2
申请日:2014-01-28
公开日:2021-01-12
发明作者:Mansour Taftaf；Jaiprakash Brijlal Sainani；Vladimir Aleksandrovich Zakharov；Gennadii Dimitrievich Bukatov；Mahendrabhai Patel Vimalkumar；Sergei Andreevich Sergeev；Martin Alexander Zuideveld；Aurora Alexandra Batinas-Geurts
申请人:Saudi Basic Industries Corporation；
IPC主号:

专利说明:

[0001] The invention relates to a catalyst composition for the polymerization of olefins. The invention also relates to a process for the preparation of said catalyst composition and to a catalyst composition obtained by that process. Furthermore, the invention relates to a catalyst system for an olefin polymerization comprising said catalyst composition, a co-catalyst and optionally an external electron donor; and a process of forming polyelefins by contacting an olefin with said catalyst system. The invention also relates to the use of said catalyst composition in the polymerization of olefins.
[0002] Ziegler-Natta catalyst systems and their components are commonly known to be suitable for the preparation of polyolefins, such as, for example, polypropylene. The term is known in the art and typically refers to catalyst systems comprising a transition metal containing a solid catalyst compound; an organo-metal compound and optionally one or more electron donating compounds (external donors). The transition metal containing a solid catalyst compound comprises a transition metal halide, i.e., titanium, chromium, vanadium halide supported on a metal or metalloid compound, such as magnesium chloride or silica. An overview of such types of catalyst is, for example, given by T. Pullukat and R. Hoff in Catal. Rev. Sci. Eng. 41, vol. 3 and 4, 389-438, 1999. It is generally known that, for example, by variation of the transition metal; the type of support; internal / external donors; the type of co-catalyst; by adding additional compounds Follows leaf 1a / 53 onals; and / or by introducing certain components at different stages, the catalyst activity, morphology and properties made by using such catalysts, such as isotacticity, can be tuned. For example, WO 96 / 32426A discloses a 3-step process for the production of a catalyst for the polymerization of an olefin, in which in the first two steps an Mg (OAlk) xCly compound of a certain morphology is prepared, and subsequently this solid Mg compound is put in contact with titanium tetrachloride, and an internal electron donation compound, which is dibutyl phthalate. However, the polyolefins obtained by using such a catalyst certainly show low yield. WO 2006 / 056338A1 discloses a process for the polymerization of propylene using a catalyst comprising a catalyst component obtained by a process in which a compound with the formula Mg (OAlk) xCly in which x is greater than 0 and less than 2, y is equal to 2-x and each Alk, independently, represents an alkyl group, a titanium tetra-alkoxide and / or an alcohol is contacted in the presence of an internal dispersant to give an intermediate reaction product and in which the intermediate reaction product is brought into contact with titanium tetrachloride in the presence of an internal donor, which is dibutyl phthalate. However, polyolefins with narrow MWD are obtained by applying the catalyst disclosed in this document. EP1838741B1 discloses a process for producing a catalyst for an olefin polymerization, in which a compound with the formula Mg (OAlk) xCly, where x is greater than 0 and less than 2, y equals 2- x and each Alk, independently, represents an alkyl group, is contacted with titanium tetra-alkoxide and / or an alcohol in the presence of an internal dispersant to give an intermediate reaction product and in which the intermediate reaction product is brought in contact with titanium tetrachloride in the presence of an internal donor. However, narrow MWD polyolefins are obtained with the catalyst disclosed in EP1838741B1. The molecular weight distribution (MWD) influences the properties of polyolefins and as such influences the end uses of a polymer; wide MWD in general improves flowability at high shear rate during processing and processing of polyolefins in applications that require rapid processing at very high matrix swelling, such as blowing and extrusion techniques.
[0003] WO 2011/106497 from Dow discloses a procatalyst composition comprising: a combination of a magnesium portion, a titanium portion and an internal electron donor comprising a certain halogenated amide ester, viz. (Ar1COOC (R3, R4) C (R1, R2) C (R5, R6) NHCOAr2, having a hydrogen substituent on amide nitrogen.
[0004] Therefore, there is currently a need in the catalyst industry to show better performance, for example, higher activity, good control of stereochemistry, higher isotacticity, higher sensitivity to hydrogen and / or allowing to obtain polyolefins in yield higher and / or having a higher molecular weight distribution.
[0005] It is thus an object of the invention to provide an improved catalyst composition for a polymerization of olefins, especially polypropylene which allows obtaining polyolefins with higher molecular weight distribution and higher yield while maintaining good isotacticity.
[0006] This objective is achieved with a catalyst composition for an olefin polymerization, which comprises a monoester and an internal donor being a compound represented by the formula (I),
where: R1, R2, R3, R4, R5 and R6 are the same or different and are independently selected from the group consisting of hydrogen, straight, branched and cyclic alkyl having a maximum of 20 carbon atoms and substituted or unsubstituted hydrocarbyl aromatic having 6 to 20 carbon atoms; R7 is selected from the group consisting of straight, branched and cyclic alkyl having a maximum of 20 carbon atoms and aromatic substituted or unsubstituted hydrocarbyl having from 6 to 20 carbon atoms; and R8 is selected from the group consisting of aromatic substituted or unsubstituted hydrocarbyl having 6 to 20 carbon atoms.
[0007] It has been surprisingly found that the catalyst composition comprising a monoester and an internal electron donor compound having formula (I) allows for the preparation of polyolefins, particularly polypropylenes (PP) having a higher molecular weight distribution, higher polymer yield and good stereospecificity, that is, high isotacticity. Polyolefins having a wide molecular weight distribution are here polyolefins, for example, polypropylene having an Mw / Mn higher than 6.5 or higher than 7 or even higher than 8, a wide molecular weight distribution being desirable in development of different grades of polymer used in certain applications, such as thermoforming, tubes, foams, films, blow molding. The amount of amorphous atactic polymer in the products obtained (for example, polypropylene), such as, for example, a maximum of 3% by weight or a maximum of 2% by weight or even less than 1% by weight of the total amount of polymer, meaning high isotacticity.
[0008] Another advantage of the present invention is that low amount of wax is formed, that is, low molecular weight polymers during the polymerization reaction, which results in reduced "viscosity" or no "viscosity" in the internal walls of the reactor. polymerization and inside the reactor. In addition, the catalyst composition according to the present invention can also be phthalate free allowing non-toxic polyolefins to be obtained, which show no harmful effect on human health and can thus be used, for example, in the food and medical industry . Furthermore, a smaller amount (2-3 times) of the compound of the formula (I) is required when the monoester is also used compared to when only the compound of the formula (I) and no monoester is used in the catalyst composition. Furthermore, the catalyst composition according to the present invention has a higher sensitivity to hydrogen (higher MFR). Summary of the present invention
[0009] The present invention relates in a first aspect to a catalyst composition for an olefin polymerization comprising a monoester and an internal electron donor represented by the formula (I) above, in which: R1, R2, R3 , R4, R5 and R6 are the same or different and are independently selected from the group consisting of hydrogen, straight, branched and cyclic alkyl having a maximum of 20 carbon atoms and aromatic substituted or unsubstituted hydrocarbyl having from 6 to 20 carbon atoms; R7 is selected from the group consisting of straight, branched and cyclic alkyl having a maximum of 20 carbon atoms and aromatic substituted or unsubstituted hydrocarbyl having from 6 to 20 carbon atoms; and R8 is selected from the group consisting of aromatic substituted or unsubstituted hydrocarbyl having 6 to 20 carbon atoms.
[0010] In one embodiment, R1, R2, R3, R4, R5 and R6 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl, trifluoromethyl and halophenyl group group.
[0011] In another embodiment R1 and R2 are each a hydrogen atom.
[0012] In another embodiment, when one of R3 and R4 has at least one carbon atom then the other between R3 and R4 is hydrogen and where when R5 and R6 has at least one carbon atom then the other between R5 and R6 is a hydrogen atom.
[0013] In another embodiment, R7 is selected from a group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl, benzyl, substituted benzyl halophenyl group.
[0014] In another embodiment, R8 is substituted or unsubstituted phenyl, benzyl, naphthyl, ortho-tolyl, para-tolyl or anisol group.
[0015] In another embodiment, the monoester is an acetate or a benzoate, preferably ethyl acetate, amyl acetate or ethyl benzoate.
[0016] In another embodiment, the catalyst comprises a support containing magnesium, a titanium compound containing halogen, said monoester and said internal electron donor according to formula (I).
[0017] In another embodiment, the catalyst composition further comprises an additional internal electron donor selected from the group consisting of diesters and diethers, preferably dibutyl phthalate or 9,9-bis-methoxymethyl-fluorene.
[0018] In another embodiment, the catalyst composition further comprises an additional internal electron donor selected from the group consisting of diesters and diethers, preferably dibutyl phthalate or 9,9-bis-methoxymethyl-fluorene, in which the ratio molar of the additional internal electron donor for magnesium of said magnesium-containing support is between 0.02 and 0.15.
[0019] In another aspect, the present invention relates to a process for the preparation of the catalyst composition, said process comprising contacting a support containing magnesium with a titanium compound containing halogen, a monoester, a first internal electron donor represented by formula (I), and optionally a second internal electron donor selected from a group consisting of diesters and diethers, where: R1, R2, R3, R4, R5 and R6 are the same or different and they are independently selected from the group consisting of hydrogen, straight, branched and cyclic alkyl having a maximum of 20 carbon atoms and aromatic substituted or unsubstituted hydrocarbyl having from 6 to 20 carbon atoms; R7 is selected from the group consisting of straight, branched and cyclic alkyl having a maximum of 20 carbon atoms and aromatic substituted or unsubstituted hydrocarbyl having from 6 to 20 carbon atoms; and R8 is selected from the group consisting of aromatic substituted or unsubstituted hydrocarbyl having 6 to 20 carbon atoms.
[0020] In one embodiment, said process comprises the steps of: i) contacting a compound R9zMgX2-z in which R9 is an aromatic, aliphatic or cycloaliphatic group containing from 1 to 20 carbon atoms, X is a halide, ez is in a range of greater than 0 and less than 2, with a silane compound containing alkoxy or aryloxy to give a first intermediate reaction product; ii) contact of the first intermediate reaction product with at least one activation compound selected from the group formed by electron donors and compounds of the formula M (OR10) vw (OR11) w, where M can be Ti, Zr, Hf, Al or Si, and M (OR10) vw (R11) w, where M is Si, each R10 and R11, independently, represent an alkyl, alkenyl or aryl group, v is the valence of M, v being either 3 or 4, ew is less than v; preferably the at least one activating compound is selected from the group formed by compounds of the formula M (OR10) vw (R11) w, where M is Si, to give a second intermediate reaction product; and iii) contact of the second intermediate reaction product with a halogen-containing Ti compound, the monoester, the compound represented by formula (I) as the first internal electron donor, and optionally the diester or diether as the second donor of internal electron.
[0021] In another aspect, the present invention relates to a catalyst composition obtained by or obtainable by the process according to the present invention.
[0022] In another aspect, the present invention relates to polymerization catalyst system comprising the catalyst composition according to the present invention or the catalyst composition obtained by or obtainable by the process of the present invention, a co-catalyst and optionally an external electron donor.
[0023] In another aspect, the present invention relates to a process of forming a polyolefin comprising a step of contacting an olefin with the present catalyst system, the olefin being preferably propylene.
[0024] In another aspect, the present invention relates to the use of the present catalyst composition comprising a monoester, a compound represented by formula (I) as a first internal electron donor, and optionally a second selected internal electron donor of a group consisting of diesters and ethers in the polymerization of olefins, in which: R1, R2, R3, R4, R5 and R6 are the same or different and are independently selected from the group consisting of hydrogen, straight, branched and cyclic alkyl having a maximum of 20 carbon atoms and aromatic substituted or unsubstituted hydrocarbyl having 6 to 20 carbon atoms; R7 is selected from the group consisting of straight, branched and cyclic alkyl having a maximum of 20 carbon atoms and aromatic substituted or unsubstituted hydrocarbyl having from 6 to 20 carbon atoms; and R8 is selected from the group consisting of aromatic substituted or unsubstituted hydrocarbyl having 6 to 20 carbon atoms. Definitions
[0025] An internal donor (also called an internal electron donor) is defined herein as an electron donating compound that is commonly described in the prior art as a reagent in the preparation of a solid catalyst component for a Ziegler catalyst system -Natta for polymerization of olefins; that is, contact of a support containing magnesium with a Ti compound containing halogen and an internal donor.
[0026] As used herein, the term "hydrocarbyl" is a substituent containing only hydrogen or carbon atoms, including saturated or unsaturated, linear or branched aliphatic radical, such as alkyl, alkenyl, and alkynyl; alicyclic radical, such as cycloalkyl, cycloalkenyl; aromatic radical, such as monocyclic or polycyclic aromatic radical, as well as their combinations, such as alkaryl and aralkyl.
[0027] As described there, the term "substituted hydrocarbyl" is a hydrocarbyl group that is substituted with one or more substitute non-hydrocarbyl groups. A non-limiting example of a non-hydrocarbyl substituent is a heteroatom. As used here, a hydrocarbon is an atom other than carbon or hydrogen. Non-limiting examples of heteroatoms include: halogens (F, Cl, Br, I), N, O, P, B, S and Si. Detailed Description of the Invention
[0028] The present invention will be discussed in more detail below.
The monoester according to the present invention can be any ester of a monocarboxylic acid known in the art. The monoester can have the formula R'-CO-OR ”, where R 'can be the same or different from R”.
[0030] R 'can be selected from the group consisting of hydrogen, straight, branched and cyclic alkyl having a maximum of 20 carbon atoms and aromatic substituted or unsubstituted hydrocarbyl having from 6 to 20 carbon atoms. In particular, R 'can be selected from the group consisting of hydrogen; straight and branched alkyl having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms and more preferably 1 to 5 carbon atoms; and cyclic alkyl having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms and more preferably 3 to 5 carbon atoms; and aromatic substituted or unsubstituted hydrocarbyl having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms.
[0031] R ”can be selected from the group consisting of straight, branched and cyclic alkyl having a maximum of 20 carbon atoms and aromatic substituted or unsubstituted hydrocarbyl having from 6 to 20 carbons. In particular, the monoester can have the formula R'-COOR ”, where R 'can be the same or different from R” and where R' can be selected from the group consisting of hydrogen; straight and branched alkyl having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms and more preferably 1 to 5 carbon atoms; and cyclic alkyl having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms and more preferably 3 to 5 carbon atoms; and aromatic substituted or unsubstituted hydrocarbyl having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms.
[0032] Suitable examples of monoesters include formates, for example, butyl formate; acetates, for example, ethyl acetate, amyl acetate and butyl acetate; acrylates, for example, ethyl acrylate, methyl methacrylate and isobutyl methacrylate; benzoates, particularly C1-C20 hydrocarbyl esters of benzoic acid, in which the hydrocarbyl group is substituted or unsubstituted with one or more substituents containing group 14, 15 or 16 heteroatom and its derivatives of C1-C20 (poly) hydrocarbyl ether preferably, C1-C4 alkyl benzoate and its derivatives alkylated on the C1-C4 ring more preferably, methyl benzoate, ethyl benzoate, propyl benzoate, p-methoxy benzoate, methyl benzoate, p-ethoxy benzoate methyl; more preferably ethyl benzoate. Other suitable examples include methyl-p-toluate and ethyl-naphthalate. Most preferably, the monoester is an acetate or a benzoate. Most preferably, the monoester is ethyl acetate, amyl acetate or ethyl benzoate.
[0033] Preferably, R1, R2, R3, R4, R5 and R6 in Formula (I) are independently selected from a group consisting of hydrogen; straight and branched alkyl with 1 to 10 carbon atoms; and cyclic alkyl having 3 to 10 carbon atoms; and aromatic substituted or unsubstituted hydrocarbyl having 6 to 10 carbon atoms. More preferably, R1, R2, R3, R4, R5 and R6 are independently selected from a group of compounds consisting of hydrogen, straight and branched C1-C10 alkyl; C3-C10 cycloalkyl; C6-C10 aryl; and group C7-C10 alkaryl and aralkyl. Even more preferably, R1, R2, R3, R4, R5 and R6 are independently selected from a group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl, trifluoromethyl and halophenyl group. More preferably, R1, R2, R3, R4, R5 and R6 are each hydrogen, methyl, ethyl, propyl, phenyl or trifluoromethyl.
[0034] Preferably, R1 and R2 are each a hydrogen atom. More preferably, R1 and R2 are each a hydrogen atom and each of R3, R4, R5 and R6 is selected from the group consisting of hydrogen, straight and branched C1-C10 alkyl; C3-C10 cycloalkyl; C6-C10 aryl; and C7-C10 alkaryl and aralkyl group; even more preferably, R3, R4, R5 and R6 are each selected from the group consisting of hydro genie, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl, trifluoromethyl and halophenyl group; more preferably, R3, R4, R5 and R6 are each hydrogen, methyl, ethyl, propyl, phenyl or trifluoromethyl.
[0035] Preferably, at least one of R3 and R4 and at least one of R5 and R6 is having at least one carbon atom, as defined above. More preferably, when one of R3 and R4 has at least one carbon atom then the other between R3 and R4 is hydrogen and where when one of R5 and R6 has at least one carbon atom then the other between R5 and R6 is hydrogen.
[0036] Preferably, R7 in Formula (I) is the same or different than any of R1, R2, R3, R4, R5 and R6 with the proviso that R7 is not a hydrogen atom.
[0037] Preferably, R7 is selected from the group consisting of straight and branched alkyl having 1 to 10 carbon atoms; and cyclic alkyl having 3 to 10 carbon atoms; and aromatic substituted or unsubstituted hydrocarbyl having 6 to 10 carbon atoms. Most preferably, R7 is selected from the group consisting of straight and branched C1-C10 alkyl; C3-C10 cycloalkyl; C6-C10 aryl; and group C7C10 alkaryl and aralkyl. Even more preferably, R7 is selected from a group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl, benzyl and substituted halophenyl and benzyl group. More preferably, R7 is methyl, ethyl, propyl, isopropyl, benzyl phenyl; and even more preferably, R7 is methyl, ethyl or propyl.
[0038] R8 in Formula (I) can be the same or different than each of R1-R7 and is preferably an aromatic substituted or unsubstituted hydrocarbyl having from 6 to 10 carbon atoms. More preferably, R8 is selected from the group consisting of C6-C10 aryl substituted or unsubstituted with, for example, an acyl halide or an alkoxide; and C7-C10 alkaryl and aralkyl group; for example, 4methoxyphenyl, 4-chlorophenyl, 4-methylphenyl. Particularly preferred, R8 is substituted or unsubstituted phenyl group, benzyl, naphthyl, ortho-tolyl, para-tolyl or anisole. More preferably, R8 is phenyl.
[0039] Preferably, R1 and R2 are each a hydrogen atom and one of R3 and R4 and one of R5 and R6 is selected from the group consisting of straight and branched C1-C10 alkyl; C3-C10 cycloalkyl; C6-C10 aryl; and C7-C10 alkaryl and aralkyl group; more preferably, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl, trifluoromethyl and halophenyl group; and most preferably, one from R3 and R4 and one from R5 and R6 is methyl.
[0040] The compound represented by formula (I) can also be called here the “first internal electron donor”.
[0041] The catalyst composition according to the present invention can further comprise an additional internal electron donor, here also called the "second internal electron donor". The additional internal donor is selected from a group consisting of diesters and diethers.
[0042] The diester can be any ester of an aromatic C6-C20 carboxylic acid or an aliphatic C1-C2 dicarboxylic acid known in the art. Suitable examples of diesters include C6-C20 aromatic or C1-C20 aliphatic substituted phthalates, for example, dibutyl phthalate, diisobutyl phthalate, diaryl phthalate and / or diphenyl phthalate; substituted aromatic C6-C20 or C1-C20 aliphatic succinates; and also substituted C6-C20 aromatic or C1-C20 aliphatic esters of malonic acid or glutaric acid. Preferably the diester is a substituted aliphatic C1-C10 phthalate, more preferably dibutyl phthalate.
[0043] The diether can be any diether known in the art. Examples of suitable ethers include aromatic C6C20 and C1-C20 aliphatic substituted ethers, for example, 2,2-diisobutyl1, 3d-methoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-ethyl-2butyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 1,1-bis (methoxymethyl) -cyclopentadiene, 1,1-bis (methoxymethyl) -2,3,4,5tetramethylcyclopentadiene; 1,1-bis (methoxymethyl) -2,3,4,5tetrafenylcyclopentadiene; 1,1-bis (methoxymethyl) indene; 1,1bis (methoxymethyl) -2,3-dimethylindene; 1,1-bis (methoxymethyl) cyclopentylindene; 9.9 bis (methoxymethyl) fluorene; 9.9 bis (methoxymethyl) 2,3,6,7-tetramethylfluorene; 9.9 bis (methoxymethyl) -2,3-benzofluorene; 9.9 bis (methoxymethyl) -2,7-diisopropylfluorene; 9.9 bis (methoxymethyl) -1.8 dichlorofluorene; 9.9 bis (methoxymethyl) -2,7-dicyclopentylfluorene; 9.9 bis (methoxymethyl) difluorofluorene; 9.9 bis (methoxymethyl) -1,2,3,4-tetrahydrofluorene; 9.9 bis (methoxymethyl) -4-tert-butylfluorene. Preferably, the diether is 9,9-bis-methoxymethyl-fluorene.
[0044] The catalyst composition according to the present invention can be the solid catalyst component of a Ziegler-Natta type of catalyst system as known in the art, also known under the term "procatalyst" and which typically comprises a support containing magnesium, a titanium compound containing halogen and an internal electron donor. Such catalyst systems are readily described in the prior art, for example, in WO 96 / 32426A, WO 2006 / 056338A1, EP 1838741B1 and US 5077357.
[0045] According to the present invention, the catalyst composition comprises a support containing magnesium, a titanium compound containing halogen, a monoester, an internal electron donor represented by formula (I), and optionally an additional internal electron donor selected from a group consisting of diesters and diethers.
[0046] Preferably, the catalyst composition of the present invention consists of a support containing magnesium, a titanium compound containing halogen, a monoester, an internal electron donor represented by formula (I), and optionally an additional internal electron donor selected from a group consisting of diesters and diethers.
[0047] Without wishing to be limited to them, particular examples of the compounds of formula (I) are the structures as shown in formulas (II) (XII). For example, the structure in Formula (II) corresponds to 4- [benzoyl (methyl) amino] pentan-2-yl benzoate]; Formula (III) to 3- [benzoyl (cyclohexyl) amino] -1-phenylbutyl benzoate; Formula (IV) to 3 [benzoyl (propan-2-yl) amino] -1-phenylbutyl benzoate; Formula (V) to 4 [benzoyl (propan-2-yl) amino] pentan-2-yl benzoate; Formula (VI) to 4 [benzoyl (methyl) amino] -1,1,1-trifluoropentan-2-yl benzoate; Formula (VII) to 3- (methylamino) -1,3-diphenylpropan-1-oldibenzoate; Formula (VIII) to 2,2,6,6-tetramethyl-5- (methylamino) heptan-3-ol dibenzoate; Formula (IX) to 4- (ethyl) aminopentan-2-yl dibenzoate; Formula (X) to 3- (methyl) aminopropan-1-ol dibenzoate; Formula (XI) to 3- (methyl) amino-2,2dimethylpropan-1-ol dibenzoate; Formula (XII) to 4- (methylamino) pentan-2yl bis (4-methoxy) benzoate). The compound of formula (II) is one of the first preferred internal electron donors in the catalyst composition according to the present invention as it has high catalytic activity and allows preparation of polyolefins having a molecular weight distribution wider than 7, high isotacticity and with high performance.



[0048] The compound according to formula (I) can be made by any method known in the art. In this regard, reference is made to J. Chem. Soc. Perkin trans. I 1994, 537-543 and to Org. Synth. 1967, 47, 44. These documents reveal a step a) of contacting a 2,4-diketone substituted with a substituted amine in the presence of a solvent to give a beta-enaminoketone; followed by step b) contacting the beta-enaminoketone with a reducing agent in the presence of a solvent to give a gamma-amino alcohol. The substituted 2,4-diketone and the substituted amine can be applied in step a) in amounts ranging from 0.5 to 2.0 moles, preferably from 1.0 to 1.2 moles. The solvent in steps a) and b) can be added in an amount of 5 to 15 volume, based on the total amount of the diketone, preferably 3 to 6 volume. The molar ratio of beta-enaminoketone to diketone in step b) can be from 0.5 to 6, preferably from 1 to 3. The molar ratio of reducing agent to beta-enaminoketone in step b) can be from 3 to 8, preferably 4 to 6; the reducing agent can be selected from the group comprising metallic sodium, NaBH4 in acetic acid, NiAl alloy. Preferably, the reducing agent is sodium metal because it is an inexpensive reagent.
[0049] The gamma-amino alcohol that can be used for the formation of compound (I) can be synthesized as described in the literature and also mentioned here above or this compound can be directly purchased commercially and used as a starting compound in a reaction for obtaining the compound represented by formula (I). In particular, gamma-amino alcohol can be reacted with a substituted or unsubstituted benzoyl chloride in the presence of a base to obtain the compound represented by formula (I) (also referred to here as step c), regardless of which gamma-amino alcohol was synthesized as described in the literature or commercially purchased). The molar ratio between substituted or unsubstituted benzoyl chloride and gamma-amino alcohol can vary from 2 to 4, preferably from 2 to 3. The base can be any basic chemical compound that is capable of deprotonating gamma-amino alcohol. Said base can have a pKa of at least 5; or at least 10 or preferably between 5 and 40, where pKa is a constant already known to the person versed as the negative logarithm of the acid dissociation constant ka. Preferably, the base is pyridine; a trialkyl amine, for example, triethylamine; or a metal hydroxide for example, NaOH, KOH. Preferably, the base is pyridine. The molar ratio between the base and the gamma-amino alcohol can vary from 3 to 10, preferably from 4 to 6.
[0050] The solvent used in any of steps a), b) and c) can be selected from any organic solvents, such as toluene, dichloromethane, 2-propanol, cyclohexane or mixtures of any organic solvents. Preferably, toluene is used in each of steps a), b) and c). Most preferably, a mixture of toluene and 2propanol is used in step b). The solvent in step c) can be added in an amount of 3 to 15 volume, preferably 5 to one volume based on the gamma-amino alcohol.
[0051] The reaction mixture in any of steps a), b) and c) can be stirred using any type of conventional stirrers for more than about 1 hour, preferably for more than about 3 hours and more preferably for more than about 10 hours, but less than about 24 hours. The reaction temperature in any of steps a) and b) can be room temperature, that is, from about 15 to about 30 ° C, preferably from about 20 to about 25 ° C. The reaction temperature in step c) can vary between 0 and 10 oC, preferably between 5 and 10oC. The reaction mixture in any of steps a), b) and c) can be refluxed for more than about 10 hours, preferably for more than about 20 hours but less than about 40 hours or until the reaction is complete (completion of the reaction can be measured by Gas Chromatography, GC). The reaction mixture from steps a) and b) can then be allowed to cool to room temperature, that is, at a temperature of from about 15 to about 30oC, preferably from about 20 to about 25oC . The solvent and any excess components can be removed in any of steps a), b) and c) by any method known in the art, such as evaporation, washing. The product obtained in any of steps b) and c) can be separated from the reaction mixture by any method known in the art, such as by extraction over metal salts, for example, sodium sulfate.
[0052] The process for preparing the catalyst composition according to the present invention comprises contacting a support containing magnesium with a titanium compound containing halogen, a monoester, a compound represented by formula (I) as a first electron donor internally and optionally, a second internal electron donor selected from a group consisting of diesters and diethers.
[0053] The support containing magnesium, titanium compounds containing halogen and internal electron donor (s) used in the process according to the present invention are known in the art as typical components of a composition of Ziegler-Natta catalyst, particularly the solid component of a catalyst and Ziegler-Nattum system. Any support containing magnesium and any titanium compounds containing halogen known in the art can be used in the process according to the present invention. For example, synthesis of such titanium-magnesium catalyst compositions with magnesium precursors containing different support, such as magnesium halides, magnesium alkyls and magnesium aryls, and also magnesium alkoxy and magnesium aryloxy compounds for the polyolefin production, particularly polypropylene production, are described, for example, in US 4978648, WO 96 / 32427A1, WO 01/23441 A1, EP 1283 222A1, EP 1222 214B1; US 5077357; US 5556820; US 4414132; US 5106806 and US 5077357 but the present process is not limited to the disclosure in these documents.
[0054] Preferably, the process for preparing the catalyst composition according to the present invention comprises the steps of: i) contacting a compound R9zMgX2-z in which R9 is aromatic, aliphatic or cycloaliphatic group containing a maximum of 20 atoms carbon, X is a halide, and z is in a range of greater than 0 and less than 2, with a silane compound containing alkoxy or aryloxy to give a first intermediate reaction product; ii) contact of the first intermediate reaction product with at least one activation compound selected from the group formed by electron donors and compounds of the formula M (OR10) vw (OR11) w, where M can be Ti, Zr, Hf, Al or Si, and M (OR10) vw (R11) w, where M is Si, each R10 and R11, independently, represent an alkyl, alkenyl or aryl group, v is the valence of M, v being either 3 or 4 ew is less than v to give a second intermediate reaction product; and iii) contact of the second intermediate reaction product with a halogen-containing Ti compound, the monoester, the compound represented by formula (I) as the first internal electron donor and optionally, the second internal electron donor selected from the group consisting of diesters and diethers. This preferred process for preparing the catalyst composition according to the present invention results in the catalyst compositions that allow obtaining polyolefins, particularly polypropylenes in high yield and having a wide molecular weight distribution and high isotacticity.
[0055] In one embodiment, the process for preparing the catalyst composition according to the present invention comprises the steps of: i) contacting a compound R9zMgX2-z where R9 is aromatic, aliphatic or cycloaliphatic group containing at most 20 carbon atoms, X is a halide, and z is in a range of greater than 0 and less than 2, with a silane compound containing alkoxy or aryloxy to give a first intermediate reaction product; ii) contact of the first intermediate reaction product with at least one activation compound selected from the group formed by the compounds of the formula M (OR10) vw (R11) w, where M is Si, each of R10 and R11, independently, represent an alkyl, alkenyl or aryl group, v is the valence of M, v being either 3 or 4 and w is less than v to give a second intermediate reaction product; and iii) contact of the second intermediate reaction product with a halogen-containing Ti compound, the monoester, the compound represented by formula (I) as the first internal electron donor and optionally, the second internal electron donor selected from the group consisting of diesters and diethers.
[0056] This preferred process for preparing the catalyst composition according to the present invention results in the catalyst compositions that allow obtaining polyolefins, particularly polypropylenes in high yield and having a wide molecular weight distribution and high isotacticity. Step i)
[0057] In step i) a first intermediate reaction product, that is, a solid support containing magnesium is prepared by contacting a compound or a mixture of compounds of the formula R9zMgX2-z where R9 is an aromatic, aliphatic or cycloaliphatic group containing at most 20 carbon atoms, X is a halide, and z is greater than 0 and less than 2, with a silane compound containing alkoxy or aryloxy, as, for example, described in WO 96/32427 A1 and WO 01 / 23441 A1. In the compound R9zMgX2-z, also called the Grignard compound, X is preferably chlorine or bromine, more preferably chlorine.
[0058] Preferably, R9 may be an aliphatic group having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms and more preferably from 1 to 5 carbon atoms. R9 can also be an aromatic group having from 6 to 20 carbon atoms, preferably from 6 to 10 carbon atoms or cycloaliphatic group containing from 3 to 20 carbon atoms, preferably from 3 to 10 carbon atoms. R9 can be an alkyl, aryl, aralkyl, alkoxide, phenoxide, etc., their mixtures with a maximum of 20 carbon atoms, preferably a maximum of 10 carbon atoms. Suitable examples of the R9 group are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, hexyl, cyclohexyl, octyl, phenyl, tolyl, xylyl, mesity and benzyl. In a preferred embodiment of the invention, R9 represents an aromatic group, for example, a phenyl group. The Grignard compound of the formula R9zMgX2-z, where z is greater than 0 and less than 2, is preferably characterized by z being about 0.5 to 1.5.
[0059] The alkane or aryloxy containing silane used in step i) is typically a compound or a mixture of compounds with the general formula Si (OR13) 4-nR14n, where n can vary from 0 to 3, preferably n is 0 up to and including 1, and each R13 and R14 groups independently represent an alkyl, alkenyl or aryl group, optionally containing one or more hetero atoms, for example, O, N, S or P, with, for example, 1 to 20 carbon atoms. Examples of suitable silane compounds include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltributoxysilane, phenyltriethoxysilane. Preferably, tetraethoxysilane is used as the silane compound in the preparation of the compound containing solid Mg in the process according to the invention. Preferably, in step i) the silane compound and the Grignard compound are introduced simultaneously into a mixing device to result in the particles of vanous morphology, especially the larger particles, as described in WO 01/23441 A1. Here, 'morphology' refers not only to the particle shape of the solid Mg compound and the catalyst made from it, but also to the particle size distribution (also characterized as a 'span') ), its fines content, dust flowability, and the apparent density of the catalyst particles. Furthermore, it is well known that a polyolefin powder produced in the polymerization process using a catalyst system based on such a catalyst component has a similar morphology as the catalyst component (the so-called "replication effect"; see, for example, S. van der Ven, Polypropylene and other Polyolefins, Elsevier 1990, pp. 8-10). Correspondingly, almost round polymer particles are obtained with a length / diameter (I / D) ratio less than 2 and with good powder flowability. Simultaneously introduced means that the introduction of the Grignard compound and the silane compound is done in such a way that the molar ratio Mg / Si does not substantially vary during the introduction of these compounds into the mixing device, as described in WO 01/23441 A1. The silane compound and the Grignard compound can be introduced continuously or by batch into the mixing device. Preferably, both compounds are introduced into the mixing device
[0060] It is explicitly noted that it is possible that the Grignard compound in step i) may alternatively have a different structure, for example, it may be a complex. Such complexes are already known to those skilled in the art; a particular example of such complexes is Fenil4Mg3Cl2.
[0061] The mixing device can take several forms; it can be a mixing device in which the silane compound is pre-mixed with the Grignard compound, the mixing device can also be a stirred reactor, in which the reaction between the compounds occurs. Preferably, the compounds are premixed before the mixture is introduced into the reactor for step i). In this way, a catalyst component is formed with a morphology that leads to polymer particles with the best morphology (high bulk density, narrow particle size distribution, (virtually) no fines, excellent flowability). The molar ratio of Si / Mg during step i) can vary within wide limits, for example, from 0.2 to 20. Preferably, the molar ratio of Si / Mg is 0.4 to 1.0.
[0062] The pre-mixing period in the reaction step indicated above can vary between wide limits, for example, from 0.1 to 300 seconds. Preferably pre-mixing is carried out for 1 to 50 seconds.
[0063] The temperature during the pre-mixing step is not specifically critical, and can, for example, vary between 0 and 80 ° C; preferably the temperature is between 10 ° C and 50 ° C. The reaction between said compounds can, for example, occur at a temperature between 20 ° C and 100 ° C; preferably at a temperature of from 0 ° C to 80 ° C. The first intermediate reaction product obtained from the reaction between the silane compound and the Grignard compound is usually purified by rinsing with an inert solvent, for example, a hydrocarbon solvent with, for example, 1 to 20 carbon atoms , such as pentane, iso-pentane, hexane or heptane. The solid product can be stored and later used as a suspension in said inert solvent. Alternatively, the product can be dried, preferably partially dried, and preferably under moderate conditions; for example, room pressure and temperature.
[0064] The first intermediate reaction product obtained by this step i) can comprise a compound of the formula Mg (OR13) xX2-x, in which the group R13 is an alkyl group containing 1 to 12 carbon atoms or an aryl group containing from 6 to 12 carbon atoms, although the present invention is not so limited. X is a halide, and x is greater than 0 and less than 2, preferably between 0.5 and 1.5. Preferably, X is chlorine or bromine and more preferably, X is chlorine.
[0065] Preferably, the group R13 contains from 1 to 8 carbon atoms. More preferably, at least one of the R13 groups represents an ethyl group. In a preferred embodiment, each R13 group represents an ethyl group.
[0066] R9zMgX2-z used in step i) can be prepared by contacting metallic magnesium with an organic halide R9X, as described in WO 96/32427 A1 and WO 01/23441 A1. All forms of metallic magnesium can be used, but preferably use is made of finely divided metallic magnesium, for example, magnesium powder. To obtain a quick reaction it is preferable to heat the magnesium under nitrogen before use. R9 and X have the same meanings as those described above. Combinations of two or more R9X organic halides can also be used.
[0067] Magnesium and organic halide R9X can be reacted with each other without the use of a separate dispersant; the organic halide R9X is then used in excess. The organic halide R9X and magnesium can also be brought into contact with each other and an internal dispersant. Examples of these dispersants are: aliphatic, alicyclic or aromatic dispersants containing a maximum of 20 carbon atoms, preferably from 4 or 6 to 20 carbon atoms.
[0068] Preferably, in this step of preparing R9zMgX2-z, an ether is also added to the reaction mixture. Examples of ethers are: diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisopropyl ether, diallyl ether, tetrahydrofuran and anisol. Dibutyl ether and / or diisoisoyl ether are preferably used. Preferably, an excess of chlorobenzene is used as the organic halide R9X. Thus, chlorobenzene serves as a dispersant as well as R9X organic halide.
[0069] The organic halide / ether ratio acts on the activity of the catalyst component. The volume ratio of chlorobenzene / dibutyl ether can, for example, vary between 75:25 and 35:65, preferably between 70:30 and 50:50.
[0070] Small amounts of iodine and / or alkyl halides can be added to cause the reaction between the magnesium metal and the organic halide R9X to proceed at a higher rate. Examples of alkyl halides are butyl chloride, butyl bromide and 1,2dibromoethane. When the organic halide R9X is an alkyl halide, iodine and 1,2-dibromoethane are preferably used.
[0071] The reaction temperature for the preparation of R9zMgX2-z is normally between 20 and 150 ° C; the reaction time is normally between 0.5 and 20 hours. After the reaction for the preparation of R9zMgX2-z is completed, the dissolved reaction product can be separated from the solid waste products. Step ii)
[0072] The first intermediate reaction product can be contacted in step ii) with at least one activation compound selected from the group formed by electron donors and compounds of the formula M (OR10) vw (OR11) w, where M can be Ti, Zr, Hf, Al or Si, and M (OR10) vw (R11) w, where M is Si, each R10 and R11, independently, represent an alkyl, alkenyl or aryl group, v is the valence of M, being either 3 or 4, ew is less than v.
[0073] In one embodiment, the first intermediate reaction product can be contacted in step ii) with at least one activation compound selected from the group formed by the compounds of the formula M (OR10) vw (R11) w, where M is Si , each R10 and R11, independently, represent an alkyl, alkenyl or aryl group, v is the valence of M, being either 3 or 4, and w is less than v.
[0074] The electron donor and the compounds of the formula M (OR10) vw (OR11) w and M (OR10) v-w (R11) w can also be called activation compounds.
[0075] Examples of suitable electron donors that can be used in step ii) are known to the skilled person and include alcohols, carboxylic acids and carboxylic acid derivatives. Preferably, an alcohol is used as the electron donor in step ii). More preferably, the alcohol is a linear or branched aliphatic having 1 to 12 carbon atoms or aromatic having 6 to 12 carbon atoms. Even more preferably, the alcohol is selected from methanol, ethanol, butanol, isobutanol, hexanol, xylenol and benzyl alcohol. Most preferably, the alcohol is ethanol or methanol.
[0076] Examples of suitable carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, isobutanoic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, tartaric acid, cyclohexanoic acid, monocarboxylic acid, cis-1,2cycloexanoic acid dicarboxylic acid, phenylcarboxylic acid, toluene carboxylic acid, naphthalene carboxylic acid, phthalic acid, isophthalic acid, tetraftalic acid and / or trimellitic acid
[0077] Groups R10 and R11 can be a cyclic alkyl or linear, branched alkenyl group or suitable groups of 1 to 20 carbon atoms, preferably 1 to 12 or 1 to 8 carbon atoms. In the case R10 and R11 are cyclic groups, they can have 3 to 20 carbon atoms. Groups can differ independently from their use. Preferably, at least one of the R10 groups represents an ethyl group. In preferred embodiments, R10 and R11 are ethyl, propyl or butyl; most preferably, all groups are ethyl groups. R10 and R11 can also be aromatic hydrocarbon groups, optionally substituted with, for example, alkyl groups and can contain, for example, from 6 to 20 carbon atoms.
[0078] Preferably, M in said activation compound is Ti or Si. Preferably, the value of w is 0, the activation compound being, for example, a titanium tetra-alkoxide containing from 4 to 32 carbon atoms . The four alkoxide groups in the compound can be the same and can be different independently. Preferably, at least one of the alkoxy groups in the compound is an ethoxy group. Most preferably the compound is a tetra-alkoxide, such as titanium tetraethoxide. Compounds containing Si suitable as activation compounds are the same as those listed above for step i).
[0079] Preferably, a Ti-based compound, for example, titanium tetraethoxide, is used together with an alcohol, such as ethanol or methanol in step ii) to give the second intermediate reaction product.
[0080] If two or more compounds were used in step ii) of the preferred process according to the invention, their order of addition is not critical, but it can affect catalyst performance which depends on the compounds used. A knowledgeable person can optimize their addition based on some experiences. The compounds of step ii) can be added together or sequentially.
[0081] The first intermediate reaction product can be contacted in any sequence with at least one electron donor and / or a compound of the formula M (OR10) v-w (OR11) w or M (OR10) v-w (R11) w. Preferably, the electron donor is first added to the first intermediate reaction product and then the compound M (OR10) v-w (OR11) w or M (OR10) v-w (R11) w is added; in this order no agglomeration of solid particles is observed. The compounds in step ii) are preferably added slowly, for example, over a period of 0.1-6, preferably over 0.5 to 4 hours, more preferably over 1 to 2.5 hours each.
[0082] The first intermediate reaction product and the electron donor and / or the compound of the formula M (OR10) vw (OR11) w or M (OR10) vw (R11) w can be contacted with an internal dispersant in step ii ). The dispersant is preferably chosen such that virtually all by-products are dissolved in the dispersant and / or act as an inert diluent for the Mg-containing support particles. Any substance known in the art that is inert to the support particles containing Mg can be used as an inert dispersant. The dispersant can be an aromatic or aliphatic hydrocarbon compound. The inert dispersant is preferably a hydrocarbon solvent and is most preferably selected from the groups of linear and branched aromatic and branched aliphatic hydrocarbon compounds with, for example, 4-20 carbon atoms. Suitable dispersants include, for example, aliphatic and aromatic hydrocarbons and halogenated aromatic solvents with, for example, 4-20 carbon atoms; alkyl and aryl halides; ethers. Preferably, the dispersant is an aliphatic hydrocarbon, more preferably pentane, iso-pentane, hexane or heptane, heptane being more preferred.
[0083] In the preferred process according to the invention the molar ratio of activating compound to the magnesium atom of the first intermediate reaction product can vary between wide limits and is, for example, between 0.02 and 1.0. Preferably the molar ratio is between 0.1 and 0.7, depending on the type of activating compound. In the process according to the invention the temperature in step ii) can be in the range of -20 ° C to 70 ° C, preferably from -10 ° C to 50 ° C, more preferably in the range between 0 ° C and 30 ° C. Preferably, at least one of the reaction components is dosed over time, for example, over 0.1 to 6, preferably over 0.5 to 4 hours, more particularly over 1 to 2.5 hours.
[0084] The second intermediate reaction product obtained can be a solid and can be washed later, preferably with the solvent also used as an inert dispersant; and then stored and later used as a suspension in said inert solvent. Alternatively, the product can be dried, preferably partially dried, preferably slowly and under moderate conditions; for example, room temperature and pressure.
[0085] Starting from a product containing solid Mg of controlled morphology, said morphology is not negatively affected during treatment with the activating compound. The second solid intermediate reaction product obtained is considered to be an addition product of the compound containing Mg and the at least one compound as defined in step ii), and is still of controlled morphology. This second intermediate reaction product being a solid magnesium containing catalyst support is subsequently contacted in step iii) with a halogen-containing titanium compound and an electron donor compound.
[0086] Preferably, the first solid intermediate reaction product is contacted with an alcohol and then with a titanium tetra-alkoxide and an internal dispersant to give a second solid intermediate reaction product. This second intermediate reaction product is then preferably contacted in step iii) with titanium tetrachloride, a monoester, the first internal donor represented by formula (I) and optionally a second internal electron donor selected from a group consisting of diesters and dieters. Step iii)
[0087] The molar ratio of Ti / Mg in the reaction between the second intermediate reaction product and the titanium compound containing halogen is preferably between 10 and 100, more preferably between 10 and 50. Titanium tetrachloride is most preferred titanium compound containing halogen.
[0088] The second intermediate reaction product can be contacted with the halogen-containing Ti compound, the monoester, the compound represented by formula (I) and optionally, the second internal electron donor in any order, at any time and at any stage that the reaction contact can be made to and by applying any method known to the person skilled in the art.
[0089] For example, the contact of the second intermediate reaction product with the Ti compound containing halogen in step iii) can be done once (which can also be called here stage I) and / or this step contact can be repeated several times, preferably it can be repeated once, twice or three times. For example, the solid intermediate reaction product can be contacted a second time (which can also be called here stage II) and / or a third time (which can also be called here III) with the halogen-containing Ti compound. Between stages I, II, III and such additional potential stages, the liquid formed during said reaction contact can be removed using any conventional methods. The monoester, the compound of the formula (I) and / or the additional internal electron donor can be added in any order and / or in any of said stages, for example, stages I, II and III.
[0090] Preferably, the second intermediate reaction product is put in contact with the Ti compound containing halogen and the monoester once, thus in stage I.
[0091] The molar ratio of monoester to magnesium can vary between 0.05 and 0.5; preferably between 0.2 and 0.4; and more preferably between 0.15 and 0.25.
[0092] Preferably, the compound of formula (I) can be added during the reaction of the second intermediate reaction product with the Ti compound containing halogen in stage I, II or III, preferably in stage II, after the introduction of monoester.
[0093] The molar ratio of the internal electron donor of formula (I) to magnesium can vary between 0.01 and 0.2. Preferably, this molar ratio is between 0.02 and 0.15; more preferably between 0.03 and 0.1; and more preferably between 0.04 and 0.05.
[0094] Preferably, the second internal donor is added during the reaction of the second intermediate reaction product with the Ti compound containing halogen in stage III or in the next stage after the internal donor addition stage of formula (I).
[0095] The molar ratio of the second internal donor to magnesium can vary between 0.02 and 0.15; and more preferably between 0.05 and 0.1.
[0096] Preferably, during contact of the second intermediate reaction product and the halogen-containing titanium compound an internal dispersant is used. The dispersant is preferably chosen such that virtually all formed side products are dissolved in the dispersant. Suitable dispersants include, for example, aliphatic and aromatic hydrocarbons and halogenated aromatic solvents with, for example, 4 to 20 carbon atoms. Examples include toluene, xylene, benzene, decane, o-chlorotoluene and chlorobenzene.
[0097] The reaction temperature during contact in step iii) the second intermediate reaction product and the halogen-containing titanium compound can preferably be between 0 ° C and 150 ° C, more preferably between 50 ° C and 150 ° C, and more than p reference between 80 ° C and 130 ° C, also depending on the boiling point of the components, such as monoester used. Most preferably, the reaction temperature is between 90 ° C and 120 ° C. The reaction product obtained can be washed, usually with an inert aromatic or aliphatic hydrocarbon or halogenated aromatic compound, to obtain the catalyst component of the invention. If desired, the reaction steps and subsequent purification can be repeated one or more times. A final wash is preferably carried out with an aliphatic hydrocarbon to result in a suspended or at least partially dried catalyst component, as described above for the other steps.
[0098] The invention later relates to the catalyst composition for a polymerization of olefins obtainable by the process according to the invention.
[0099] The invention also relates to a polymerization catalyst system which comprises the catalyst composition according to the invention and a co-catalyst. Preferably, the catalyst system also comprises an external electron donating compound, also called an external electron donor, or simply external donor. The main function of this external donor compound is to effect the stereoselectivity of the catalyst system in the polymerization of olefins having 3 or more carbon atoms, and therefore, it can also be called a selectivity control agent. Preferably, the co-catalyst is an organometallic compound containing a group 1, 2, 12 or 13 metal from the Periodic System of Elements (Handbook of Chemistry and Physics, 70th Edition, CRC Press, 1989-1990), in which the system it subsequently comprises an external electron donor.
[0100] The invention subsequently relates to a process of forming a polyolefin by contacting at least one olefin with a polymerization catalyst system comprising the catalyst composition according to the present invention.
[0101] Preferably, the polyolefin made using the catalyst system of the present invention is polypropylene. It is an advantage of the present invention that polypropylene obtainable by using said catalyst has a wide molecular weight distribution and a low amount of atactic fraction and is obtained in high yield.
[0102] The preparation of polyolefins can take place by polymerizing one or more olefins simultaneously and / or successively in the presence of a catalyst system comprising the catalyst according to the invention, a co-catalyst and optionally an external donor. The olefin according to the invention can be selected from mono and di-olefins containing from 2 to 10 carbon atoms, such as, for example, ethylene, propylene, butylene, hexene, octene and / or butadiene. According to a preferred embodiment of the invention the olefin is a propylene or a mixture of propylene and ethylene, to result in a propylene homopolymer or copolymer. A propylene copolymer here is intended to include both so-called copolymers with a relatively low comonomer content, for example, up to 10 mol%, as well as so-called impact copolymers comprising higher comonomer contents, for example, of 5 to 80 mol%, more typically 10 to 60 mol%. Impact copolymers are actually combinations of different propylene polymers; such copolymers can be made in one or two reactors and can be combinations of a first component of low comonomer and high crystallinity, and a second component of high comonomer having low crystallinity or rubber-like properties. Such random and impact copolymers are well known to the person skilled in the art.
[0103] In general, the co-catalyst is an organometallic compound containing a metal of group 1, 2, 12 or 13 of the Periodic System of Elements (Handbook of Chemistry and Physics, 70th Edition, CRC Press, 19891990). Preferably, the co-catalyst is an organoaluminium compound. The organoaluminium compound can be, for example, a compound having the formula AIR153, where each R15 independently represents an alkyl group with, for example, 110 carbon atoms or an aryl group with, for example, 6-20 atoms of carbon. Examples of a suitable organoaluminium compound are trimethylaluminum, triethylalumin, triisobutylaluminum, and / or trioctylalumin. Preferably, the co-catalyst is triethyl aluminum.
[0104] Examples of suitable external donors include organo-silicon compounds. Mixtures of external donors can also be used. Examples of organo-silicon compounds that are suitable as an external donor are compounds or mixtures of compounds of the general formula Si (OR16) 4-nR17n, where n can be 0 to 2 preferably n is 1 or 2 as higher values tall have no positive effect on stereospecificity, and each R16 and R17, independently, represents an alkyl or aryl group, optionally containing one or more heteroatoms, for example, O, N, S or P, with, for example, 1- 20 carbon atoms, as defined above for R13 and R14. Examples of suitable compounds include the silane compounds that can be used in step i), as described above. Preferably the organo-silicon compound used as an external donor is n-propyl trimethoxysilane. The molar ratio of the metal of the co-catalyst to titanium in the polymerization catalyst system during polymerization can vary, for example, from 5 to 2000. Preferably this ratio is between 50 and 300.
[0105] The aluminum / external donor molar ratio in the polymerization catalyst system is preferably between 1 (if less than 1 no polymerization occurs) and 200; more preferably between 5 and 100.
[0106] Preferably, no external donor is used in said catalyst system when higher molecular weight distribution and higher polymer yield are obtained.
[0107] The polymerization process can be carried out in the gas phase or in the liquid phase (in bulk or paste). In the case of polymerization in a paste (liquid phase) a dispersing agent is present. Suitable dispersing agents include, for example, n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and liquid propylene. The polymerization conditions of the process according to the invention, such as, for example, the polymerization time and temperature, monomer pressure, prevention of catalyst contamination, choice of polymerization medium in pasty processes, the use of other ingredients ( such as hydrogen) to control molar mass of polymer, and other conditions well known to persons skilled in the art. The polymerization temperature can vary within wide limits and is, for example, for propylene polymerization, between 0 ° C and 120 ° C, preferably between 40 ° C and 100 ° C. The pressure during (co) polymerization (propylene) is, for example, between 0.1 and 6 MPa, preferably between 0.5 to 3 MPa.
[0108] The molar mass of the polyolefin obtained during polymerization can be controlled by adding hydrogen during polymerization or any other agent known to be suitable for the purpose. Polymerization can be carried out in a continuous or batch mode. Pasty, mass and gas phase polymerization processes, multi-stage processes for each of these types of polymerization processes, or combinations of the different types of polymerization processes and in a multi-stage process are contemplated here. Preferably the polymerization process is a single-stage gas phase process or a multi-stage process, for example, a two-stage gas phase process in which at each stage a gas phase process is used.
[0109] Examples of gas phase polymerization processes include both agitated bed reactors and fluidized bed reactor systems; such processes are well known in the art. Typical gas phase alpha-olefin polymerization reactor systems comprise a reactor vessel to which alpha-olefin monomer (s) and a catalyst system can be added and which contains an agitated bed of developing polymer particles .
[0110] The present invention later relates to the use of a monoester, compound (I) as a first internal electron donor and optionally a second internal electron donor selected from the group consisting of diesters and diethers in a catalyst composition for polymerization of olefins. Polyolefins with improved properties, such as having a wide molecular weight distribution, high isotacticity and high yield are produced with the said catalyst composition.
[0111] It is noted that the invention relates to all possible combinations of characteristics reported in the claims. Features described in the description can be further combined.
[0112] Although the invention has been described in detail for the purposes of illustration, it is understood that such detail is only for that purpose and variations can be made there by those skilled in the art without departing from the spirit and scope of the invention as defined in claims.
[0113] It is further observed that the invention relates to all possible combinations of characteristics described here, particularly preferred are those combinations of characteristics that are present in the claims.
[0114] It is further noted that the term 'comprising' does not exclude the presence of other elements. However, it should also be understood that a description of a product comprising certain components also reveals a product consisting of these components. Similarly, it should also be understood that a description of a process comprising certain steps also reveals a process that consists of these steps.
[0115] The invention will be further elucidated with the following examples without being limited to them. Examples Preparation of 4- [benzoyl (methyl) amino] pentan-2-yl benzoate (AB) Step a)

[0116] 40% solution of monomethylamine in water (48.5 g, 0.625 mol) was added dropwise to a stirred solution of substituted pentane-2,4-dione (50 g, 0.5 mol) in toluene ( 150 ml. After the addition, the reaction mass was stirred at room temperature for 3 hours and then refluxed. During reflux the water formed was azeotropically removed using a Dean-stark trap. Then the solvent was removed under reduced pressure to give 4- (methylamino) pent-3-en-2-one, 53.5 g (95% yield), which had been directly used for the reduction. Step b)

[0117] 4- (methylamino) -pent-3-en-2-one (100 g) was added to a stirred mixture of 1000 ml of 2-propanol and 300 ml of toluene. To this solution, small pieces of 132 g metallic sodium were gradually added at a temperature between 25 and 60 oC. The reaction mass was refluxed for 18 h. The dough was cooled to room temperature and poured into cold water and extracted with dichloromethane. The extract was dried over sodium sulfate, filtered and then evaporated under reduced pressure to give 65 g of oil of 4 (methylamino) pentan-2-ol (isomer mixture) (63% yield). Step c)

[0118] 4- (methylamino) pentan-2-ol (10 g) was added to a mixture of pyridine (16.8 g) and toluene (100 ml). The dough was cooled to 10oC and benzoyl chloride (24 g) was added dropwise. The mixture was refluxed for 6 h. The mixture was then diluted with toluene and water. The organic layer was washed with diluted HCl, bicarbonate saturated with water and brine solution. The organic layer was dried over sodium sulfate, filtered and then evaporated under reduced pressure. The residue was purified by flash chromatography to form 25 g of product as a thick oil (90% yield). The product was characterized by 1H NMR and 13C NMR: m / z = 326.4 (m + 1), 1H NMR (300 MHz, CDCl3) δ = 7.95 7.91 (m, 1H), 7.66 7 , 60 (m, 2H), 7.40 7.03 (m, 5H), 6.78 6.76 (m, 2H), 4.74 5.06 (br m, 1H), 3.91 3, 82 (m, 1H), 2.83-2.56 (ddd, 3H), 2.02 1.51 (m, 1H), 1.341.25 (dd, 1H), 1.13-1.02 (m , 6H); 13C NMR (75 MHz, CDCl3) δ = 170.9, 170.4, 170.3, 164.9, 164.6, 135.9, 135.8, 135.2, 131.8, 131.7, 131.6, 129.6, 129.4, 129.3, 128.9, 128.4, 128.3, 128.2, 128.0, 127.7, 127.3, 127, 2, 127.1, 127.0, 125.7, 125.6, 125.0, 124.9, 68.3, 67.5, 67.3, 49.8, 49.4, 44.9, 44.4, 39.7, 39.0, 38.4, 38.3, 30.5, 29.8, 25.5, 25.1, 19.33, 19.1, 18.9, 18, 3, 17.0, 16.8, 16.7.
[0119] By applying the same preparation method, internal electron donors as described and characterized in table 1 were also obtained: Table 1
Example 1 A. Grignard formation step This step was carried out as described in Example XVI of EP 1 222 214 B1.
[0120] A 9 l volume stainless steel reactor was filled with 360 g magnesium powder. The reactor was placed under nitrogen. The magnesium was heated to 80 ° C for 1 hour, after which a mixture of dibutyl ether (1 liter) and chlorobenzene (200 ml) was added. Then iodine (0.5 g) and n-chlorobutane (50 ml) were successively added to the reaction mixture. After the iodine color had disappeared, the temperature was raised to 94 ° C. Then a mixture of dibutyl ether (1.6 liters) and chlorobenzene (400 ml) was added slowly over 1 hour, and then 4 liters of chlorobenzene was slowly added over 2.0 hours. The temperature of the reaction mixture was maintained in the range of 98 to 105oC. The reaction mixture was stirred for another 6 hours at 97-102 ° C. Then stirring and heating were stopped and the solid material was allowed to settle for 48 hours. By decanting the solution above the precipitate, a solution of reaction product A of phenylmagnesium chloride was obtained with a concentration of 1.3 moles of Mg / l. This solution was used in the preparation of another catalyst. B. Preparation of the first intermediate reaction product
[0121] This step was performed as described in Example XX of EP 1 222 214 B1, except that the dosed delivery temperature of the reactor was 35 ° C, the delivery time of the outlet was 360 min and the propellant agitator was hectic. 250 ml of dibutyl ether was introduced into a 1 liter reactor. The reactor was equipped with a stirrer with propellant and two deflectors. The reactor was thermo-regulated at 35 ° C.
[0122] The reaction product solution from step A (360 ml, 0.468 mol Mg) and 180 ml of a solution of tetraethoxysilane (TES) in dibutyl ether (DBE), (55 ml of TES and 125 ml of DBE) , were cooled to 10 ° C, and then dosed simultaneously to a 0.45 ml volume mixing device provided with a shaker and a jacket. Dosed administration time was 360 min. Thereafter the pre-mixed reaction product A and the TES solution were introduced into a reactor. The mixing device (mini-mixer) was cooled to 10 ° C by means of cold water circulating in the mini-mixer jacket. The stirring speed in the mini mixer was 1000 rpm. The stirring speed in the reactor was 350 rpm at the beginning of the dosed administration and was gradually increased to 600 rpm at the end of the dosed administration stage.
[0123] Upon completion of the dosed administration of the reaction mixture, it was heated to 60 ° C and maintained at this temperature for 1 hour. Then the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decantation. The solid substance was washed three times using 500 ml of heptane. As a result, a pale yellow solid substance, reaction product B (the first solid intermediate reaction product; the support), was obtained, it was suspended in 200 ml of heptane. The average support particle size was 22 μm and the small distance value (d90 -d10) / d50 = 0.5. C. Preparation of the second intermediate reaction product
[0124] Support activation was performed as described in Example IV of WO / 2007/134851 to obtain the second intermediate reaction product.
[0125] In the atmosphere of inert nitrogen at 200C a 250 ml glass vial equipped with a mechanical stirrer and filled with a paste of 5 g of reaction product B dispersed in 60 ml of heptane. Subsequently, a solution of 0.22 ml of ethanol (EtOH / Mg = 0.1) in 20 ml of heptane is dosed with stirring for 1 hour. After keeping the reaction mixture at 200C for 30 minutes, a solution of 0.79 ml of titanium tetraethoxide (TET / Mg = 0.1) in 20 ml of heptane was added for 1 hour.
[0126] The paste was slowly allowed to warm up to 300C for 90 min and was kept at that temperature for another 2 hours. Finally, the supernatant liquid is decanted from the solid reaction product (the second intermediate reaction product; activated support) which was washed once with 90 ml of heptane at 300 ° C. D. Preparation of the catalyst component
[0127] A reactor was placed under nitrogen and 125 ml of titanium tetrachloride were added to it. The reactor was heated to 90oC and a suspension, containing about 5.5 g of the activated support in 15 ml of heptane, was added to it with stirring. The reaction mixture was maintained at 90oC for 10 min. Then add 0.866 g of ethyl acetate (EA / Mg = 0.25 mol). The reaction mixture was maintained for 60 min (catalyst preparation stage I). Then the stirring was stopped and the solid substance was left to deposit. The supernatant was removed by decantation, after which the solid product was washed with chlorobenzene (125 ml) at 1000C for 20 min. Then the washing solution was removed by decantation, after which a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added. The temperature of the reaction mixture was increased to 1150C and 0.64 g of 4- [benzoyl (methyl) amino] pentan-2-yl benzoate (aminobenzoate, AB, AB / Mg = 0.05 mol) in 2 ml of chlorobenzene was added to a reactor. Then the reaction mixture was maintained at 1150C for 30 min (stage II of the catalyst preparation). After which the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decantation, after which a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added. The reaction mixture was kept at 1150C for 30 min (stage III of the catalyst preparation), after which the solid substance was left to deposit. The supernatant was removed by decanting and the solid was washed five times using 150 ml of heptane at 600 ° C, after which the catalyst component, suspended in heptane, was obtained. E. Polymerization of propylene
[0128] Propylene polymerization was carried out in a stainless steel reactor (with a volume of 0.7 I) in heptane (300 ml) at a temperature of 700C, a total pressure of 0.7 MPa and the presence of hydrogen (55 ml) ) for 1 hour in the presence of a catalyst system comprising the catalyst component according to step D, triethyl aluminum and n-propyltrimethoxysilane. The concentration of the catalyst component was 0.033 g / l; the concentration of triethyl aluminum was 4.0 mmoles / l; the concentration of n-propyltrimethoxysilane was 0.2 mmol / l.
[0129] Data on catalyst performance in propylene polymerization are shown in Table 2. In all Tables here, monoester (ME) refers to EA, EB or AA. Example 1a
[0130] Example 1a was carried out in the same way as Example 1, but in step E no n-propyltrimethoxysilane was used. Example 2
[0131] Example 2 was performed in the same way as Example 1, but AB / Mg = 0.04 in step D was used instead of AB / Mg = 0.05. Example 3
[0132] Example 3 was performed in the same way as Example 2, but 1.27 g of amyl acetate (AA / Mg = 0.25) in step D was used instead of ethyl acetate (EA / Mg = 0.25 ). Example 4
[0133] Example 4 was performed in the same way as Example 1, but in step D 0.886 g of ethyl benzoate (EB / Mg = 0.15) at 1000C and AB / Mg = 0.15 were used instead of EA / Mg = 0.25 to 900C and AB / Mg = 0.05, respectively. Example 5
[0134] Example 5 was performed in the same way as Example 4, but AB / Mg = 0.05 in step D was used instead of AB / Mg = 0.15. Example 5a
[0135] Example 5a was performed in the same way as Example 5, but in step E no n-propyltrimethoxysilane was used. Example 6
[0136] Example 6 was performed in the same way as Example 4, but AB / Mg = 0.04 in step D was used instead of AB / Mg = 0.15. Comparative example A (CE-A)
[0137] CE-A was performed in the same manner as Example 1, but 0.61 g of 4- (phenylcarbonyl) amino] pentan-2-yl benzoate (group AB-H: NH is present in AB instead of the group N-Me) in AB-H / Mg = 0.05 in step D was used instead of AB / Mg = 0.05. Comparative example B (CE-B)
[0138] CE-B was performed in the same way as CE-A, but in step E no n-propyltrimethoxysilane was used. Comparative example C (CE-C)
[0139] CE-C was performed in the same way as Example 1, but in AB it was added in step D. Comparative example D (CE-D)
[0140] CE D was performed in the same way as Example 5, but AB-H / Mg = 0.05 in step D was used instead of AB / Mg = 0.05. Comparative example E (CE-E)
[0141] CE-E was performed in the same way as CE-D, but in step E no n-propyltrimethoxysilane was used. Comparative example F (CE-F)
[0142] CE-F was performed in the same way as Example 4, but in AB it was added in step D. Comparative example G (CE-G)
[0143] CE-G was carried out in the same manner as Example 1, but the preparation of the catalyst component in step D was carried out as follows.
[0144] A reactor was placed under nitrogen and 125 ml of titanium tetrachloride was added to it. The reactor was heated to 1000C and a suspension, containing about 5.5 g of the activated support in 15 ml of heptane, was added to it with stirring. Then the temperature of the reaction mixture was increased to 1100C for 10 min and 1.92 g of 4- [benzoyl (methyl) amino] pentan-2-yl benzoate (aminobenzoate, AB, AB / Mg = 0.15) in 3 ml of chlorobenzene was added to a reactor. Then the reaction mixture was maintained at 1150C for 105 min (stage I of the catalyst preparation). Then the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decantation, after which the solid product was washed with chlorobenzene (125 ml) at 1000C for 20 min. Then the washing solution was removed by decantation, after which a mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5 ml) was added. The reaction mixture was maintained at 1150C for 30 min (stage II of the catalyst preparation), after which the solid substance was allowed to settle. The supernatant was removed by decantation, and the last treatment was repeated again (stage III of the catalyst preparation). The obtained solid substance was washed five times using 150 ml of heptane at 600 ° C, after which the catalyst component, was suspended in heptane, was obtained. Comparative example H (CE-H)
[0145] CE-H was performed in the same way as CE-G, but in step E no n-propyltrimethoxysilane was used.
[0146] Data on the performance of the catalyst in the polymerization of propylene (Examples 1-8 and from CE-A to CE-H) are presented in Table 2. Example 7
[0147] Example 7 was performed in the same way as step D in Example 1, but 5 g of Mg (OEt) 2 (Aldrich grade) when the support containing Mg, 0.97 g of ethyl acetate (EA / Mg = 0 , 25 mol) and 0.72 g of AB (AB / Mg = 0.05) were used instead of 5.5 g of the activated support, 0.866 g of ethyl acetate and 0.64 g of AB.
[0148] Data on the performance of the catalyst in the propylene polymerization are presented in Table 4. Comparative example I (CE-I)
[0149] CE-I was performed in the same way as step D in CE-G, but 5 g of Mg (OEt) 2 (Aldrich grade) when the support containing Mg and 2.15 g of AB (AB / Mg = 0 , 15) were used instead of 5.5 g of activated support and 1.92 g of AB. Example 8
[0150] Example 8 was performed in the same way as step D in Example 1, but 5 g of the support containing Mg prepared according to US 5077357, 0.64 g of ethyl acetate (EA / Mg = 0.25 mol) and 0.48 g of AB (AB / Mg = 0.05) was used instead of 5.5 g of the activated support, 0.866 g of ethyl acetate and 0.64 g of AB. Comparative example J (CE-J)
[0151] CE-J was performed in the same way as step D in CE-G, but 5 g of the support containing Mg prepared according to US 5077357 and 1.43 g of AB (AB / Mg = 0.15) were used instead of 5.5 g of activated support and 1.92 g of AB.
[0152] Data on the performance of the catalyst in the polymerization of propylene (Examples 7-8 and from CE-I and CE-J) are presented in Table 3. Example 9
[0153] Example 9 was carried out in the same way as Example 5, but III stage of the preparation of catalyst in step D was carried out in the presence of 0.54 g of di-n-butylphthalate (DBP / Mg = 0.05) when the one another internal donor ID2. After removal of the supernatant stage III without any donor it was repeated once again (as stage of the preparation of catalyst IV). Example 9a
[0154] Example 9a was performed in the same way as Example 9, but in step E no n-propyltrimethoxysilane was used. Example 10
[0155] Example 10 was performed in the same way as Example 9, but AB / Mg = 0.018 and DBP / Mg = 0.1 in step D was used instead of AB / Mg = 0.05 and DBP / Mg = 0 , 05. Example 11
[0156] Example 11 was performed in the same way as Example 9, but 0.5 g of 9,9-bis-methoxymethyl-fluorene (flu) (flu / Mg = 0.05) in step D was used instead of 0.54 g of di-n-butyl phthalate (DBP / Mg = 0.05). Example 11a
[0157] Example 11a was performed in the same way as Example 11, but in step E no n-propyltrimethoxysilane was used. Example 12
[0158] Example 12 was performed in the same way as Example 11, but AB / Mg = 0.025 in step D was used instead of AB / Mg = 0.05. Example 12a
[0159] Example 12a was performed in the same way as Example 11, but in step E no n-propyltrimethoxysilane was used.
[0160] Data on the performance of the catalyst in the propylene polymerization (Examples 9-12) are shown in Table 4. Table 2

Table 3
* = catalyst support prepared according to the procedure described in US 5077357 Table 4

Abbreviations and measurement methods: PP yield, kg / g of cat is the amount of polypropylene obtained per gram of catalyst component. APP,% by weight is the weight percentage of atactic polypropylene. Atactic PP is the fraction of PP soluble in heptane during polymerization. APP was determined as follows: 100 ml of the filtrate (y ml) obtained by separating the polypropylene powder (xg) and the heptane was dried over a steam bath and then under vacuum at 60 ° C. That one supplied zg of atactic PP. The total amount of atactic PP (qg) is: (y / 100) * z. The weight percentage of atactic PP is: (q / (q + x)) * 100%. XS,% by weight is soluble xylene, measured according to ASTM D 5492-10. MFR is the melt flow rate as measured at 230 ° C with 2.16 kg of load, measured according to ISO 1133. Mw / Mn: Molecular weight of polymer and its distribution (MWD) were determined by Waters 150 oC chromotograph of gel permeation combined with a Viscotek 100 differential viscometer. Chromatograms were performed at 140 ° C using 1,2,4-trichlorobenzene as a solvent with a flow rate of 1 ml / min. The refractive index detector was used to collect the signal for molecular weights. The 1H-NMR and 13C-NMR spectra were recorded on a 300 MHz Varian Mercury NMR spectrometer, using deuterated chloroform as a solvent.
[0161] In addition to the higher molecular weight distribution and high isotacticity shown, catalysts prepared with monoester and AB as the internal donor show significantly (2-3 times) higher activity compared to the catalyst prepared with AB without monoester. In addition, using monoester significantly decreases (3 times) the amount of AB required for the preparation of the catalysts.
[0162] Polymerizations without an external donor compared to those with n-propyltrimethoxysilane as external donor show that the polymer yield increases; sensitivity to hydrogen (MFR values) increases; MWD of polymers (Mw / Mn values) are similar or slightly wider; and the stereospecificity of catalysts containing AB is good (APP and XS values are similar or increase insignificantly).
[0163] The addition of diester (DBP) as the second internal donor in catalyst composition allows increased sensitivity to hydrogen (MFR values) in broad MWD (Ex. 9 and Ex. 10) and increased sensitivity to external donor ( compare APP and XS values in Ex. 9 and Ex. 9a).
[0164] The addition of 1,3-diether (flu) as the second internal donor in the catalyst composition allows an increase in hydrogen and obtaining polymers with increased isotacticity (minimum XS values) can be produced (Ex. 11-12) .
[0165] By using a known internal electron donor (AB-H), Mw / Mn values are lower, the atactic fraction is higher and / or the polymer yields are lower in the polymers then obtained for the internal donor according to the present invention.

权利要求:
Claims (14)
[0001]
1. Catalyst composition for the polymerization of olefins, characterized by the fact that it comprises a monoester and an internal electron donor represented by the formula (I),
[0002]
2. Composition according to claim 1, characterized by the fact that R1, R2, R3, R4, R5 and R6 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert- butyl, phenyl, trifluoromethyl and halophenyl, preferably where R1 and R2 are each a hydrogen atom.
[0003]
3. Composition according to claim 1 or 2, characterized by the fact that when one of R3 and R4 has at least one carbon atom, then the other between R3 and R4 is hydrogen and in which, when R5 and R6 has at least one carbon atom, so the other one between R5 and R6 is a hydrogen atom.
[0004]
4. Composition according to any one of claims 1 to 3, characterized by the fact that R7 is selected from a group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl, benzyl, substituted benzyl and halophenyl and / or where R8 is substituted or unsubstituted phenyl group, naphthyl, ortho-tolyl, para-tolyl or anisole.
[0005]
5. Composition according to any one of claims 1 to 4, characterized in that the monoester is an acetate or a benzoate, preferably ethyl acetate, amyl acetate or ethyl benzoate.
[0006]
6. Composition according to any one of claims 1 to 5, characterized by the fact that it comprises a support containing magnesium, a titanium compound containing halogen, said monoester and said internal electron donor according to formula ( I).
[0007]
7. Composition according to any one of claims 1 to 6, characterized by the fact that it further comprises an additional internal electron donor selected from the group consisting of diesters and diethers, preferably dibutyl phthalate or 9,9- bismetoxymethyl-fluorene.
[0008]
8. Composition according to claim 7, characterized by the fact that the molar ratio of the additional internal electron donor to magnesium of said magnesium-containing support is between 0.02 and 0.15.
[0009]
9. Process for the preparation of the catalyst composition, as defined in any one of claims 1 to 8, characterized in that it comprises the contact of a support containing magnesium with a halogen-containing titanium compound, a monoester, a first donor internal electron represented by formula (I), and optionally a second internal electron donor selected from a group consisting of diesters and diethers,
[0010]
10. Process according to claim 9, characterized by the fact that it comprises the steps of: (i) contacting a compound R9zMgX2-z in which R9 is aromatic, aliphatic or cycloaliphatic group containing from 1 to 20 carbon atoms -bono, X is a halide, and z is in a range of greater than 0 and less than 2, with a silane compound containing alkoxy or aryloxy to give a first intermediate reaction product; (ii) contacting the first intermediate reaction product with at least one activation compound selected from the group formed by electron donors and compounds of the formula M (OR10) vw (OR11) w, where M can be Ti, Zr, Hf, Al or Si, and M (OR10) vw (R11) w, where M is Si, each R10 and R11, independently, represents an alkyl, alkenyl or aryl group, v is the valence of M, v being either 3 or 4 , ew is less than v; preferably said at least one activating compound is selected from the group formed by the compounds of the formula M (OR10) vw (R11) w, where M is Si, to give a second intermediate reaction product; and (iii) contacting the second intermediate reaction product with a halogen-containing Ti compound, the monoester, the compound represented by formula (I) as the first internal electron donor, and optionally the diester or diether as the second electron donor internal.
[0011]
11. Catalyst composition, characterized by the fact that it is obtainable by the process, as defined in claim 9 or 10.
[0012]
12. Polymerization catalyst system, characterized in that it comprises the catalyst composition, as defined in any one of claims 1 to 8 or 11 or the catalyst composition obtainable by the process, as defined in claim 9 or 10, a co -catalyst and optionally an external electron donor.
[0013]
13. Polyolefin production process, characterized by the fact that it comprises a step of contacting an olefin with the catalyst system, as defined in claim 12, the olefin being preferably propylene.
[0014]
Use of the catalyst composition, as defined in any one of claims 1 to 9 or 12, comprising a monoester, a compound represented by formula (I) as a first internal electron donor, and optionally a second selected internal electron donor of a group consisting of diesters and diethers, Formula (I) in which: R1, R2, R3, R4, R5 and R6 are the same or different and are independently selected from the group consisting of hydrogen, straight, branched and cyclic alkyl having a maximum of 20 carbon atoms and hydrocarbyl substituted or unsubstituted aromatics having 6 to 20 carbon atoms; R7 is selected from the group consisting of straight, branched and cyclic alkyl having a maximum of 20 carbon atoms and aromatic substituted or unsubstituted hydrocarbyl having from 6 to 20 carbon atoms; and R8 is selected from the group consisting of aromatic substituted or unsubstituted hydrocarbyl having 6 to 20 carbon atoms; characterized by the fact that it is in the polymerization of olefins.

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法律状态:
2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-10-27| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-01-12| 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 28/01/2014, OBSERVADAS AS CONDICOES LEGAIS. |

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2021-04-20| B09W| Correction of the decision to grant [chapter 9.1.4 patent gazette]|Free format text: REFERENCIA: RPI 2599 DE 27.10.2020 - CODIGO 9.1 |

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2021-11-23| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 8A ANUIDADE. |

优先权:

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申请号 | 申请日 | 专利标题

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EP13000492|2013-01-31|

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EP13000481|2013-01-31|

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EP13000492.2|2013-01-31|

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EP13199160|2013-12-20|

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EP13199147.3|2013-12-20|

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EP13199147|2013-12-20|

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EP13199160.6|2013-12-20|

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US201461927034P| true| 2014-01-14|2014-01-14|

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US201461927029P| true| 2014-01-14|2014-01-14|

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US61/927,034|2014-01-14|

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US61/927,029|2014-01-14|

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PCT/EP2014/051609|WO2014118164A1|2013-01-31|2014-01-28|Catalyst composition for polymerization of olefins|

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