WO1998006759A9 - Catalyseurs zwitterion ansa metallocene du groupe iv pour la polymerisation d'alpha-olefines - Google Patents
Catalyseurs zwitterion ansa metallocene du groupe iv pour la polymerisation d'alpha-olefinesInfo
- Publication number
- WO1998006759A9 WO1998006759A9 PCT/US1997/013793 US9713793W WO9806759A9 WO 1998006759 A9 WO1998006759 A9 WO 1998006759A9 US 9713793 W US9713793 W US 9713793W WO 9806759 A9 WO9806759 A9 WO 9806759A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- substituted
- unsubstituted
- alkyl
- aryl
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 12
- 239000004711 α-olefin Substances 0.000 title abstract description 7
- 239000012968 metallocene catalyst Substances 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims description 41
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 35
- 125000003545 alkoxy group Chemical group 0.000 claims description 24
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 20
- 150000001336 alkenes Chemical class 0.000 claims description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 14
- 229910052796 boron Inorganic materials 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Chemical group 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 9
- 150000004678 hydrides Chemical class 0.000 claims description 9
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910021480 group 4 element Inorganic materials 0.000 claims description 4
- 229910021478 group 5 element Inorganic materials 0.000 claims description 4
- 229910021476 group 6 element Inorganic materials 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 21
- 125000000217 alkyl group Chemical group 0.000 claims 5
- 125000001153 fluoro group Chemical group F* 0.000 claims 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003426 co-catalyst Substances 0.000 abstract description 9
- 150000001450 anions Chemical class 0.000 abstract description 4
- 150000001768 cations Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003446 ligand Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000003775 Density Functional Theory Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 238000006713 insertion reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910007928 ZrCl2 Inorganic materials 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007068 beta-elimination reaction Methods 0.000 description 1
- 239000011951 cationic catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Definitions
- ZAM Group IV Zwitterion Ansa Metallocene (ZAM) Catalysts For Alpha-Olefin Polymerization
- the present invention generally relates to olefin polymerization catalysts, and more specifically to single component metallocene catalysts for ⁇ -olefin polymerization.
- catalysts require an anionic co-catalyst (or a catalyst activator) , typically perfluorophenylborates or methyl aluminoxane (MAO) , to generate the catalytically active cationic fourteen electron d° species .
- anionic co-catalyst typically perfluorophenylborates or methyl aluminoxane (MAO)
- MAO-based systems predominate in industrial applications.
- MAO must be present in large molar excess (200-2000 times that of the metallocene catalyst) , its presence accounts for over 50% of the cost of the catalytic system. In addition to the increased expense, little is known about MAO's structure or role in the polymerization reaction. Moreover, because MAO may also provide an additional route for chain termination (via chain transfer to the trimethyl aluminum) , this complicates the design of more selective catalysts.
- Another approach is to incorporate a counter anion for a Group IV catalyst directly into the ligand.
- Jordan, et al . (Crowther, et al . , J. Am . Chem. Soc . 113:1455 (1991)) prepared catalyst in which one cyclopentadienyl (Cp) ligand is replaced by a dianionic dicarbolide ligand.
- Cp cyclopentadienyl
- the resulting complex was expected to be capable of ⁇ -olefin polymerization.
- these complexes readily undergo ⁇ - elimination, have low activity, and only oligomerize polypropylene.
- Figure 1 illustrates the result of energy calculations comparing a zwitterion ansa metallocene (ZAM) catalyst with a standard Ziegler-Natta catalyst for each step of olefin polymerization.
- ZAM zwitterion ansa metallocene
- Figure 2 illustrates transition state enthalpies for two ZAM catalysts and a standard Ziegler-Natta catalyst .
- ZAM zwitterion ansa metallocene
- M is selected from a group consisting of Group III, Group IV, Group V, and Group VI elements
- E is boron or aluminum
- R x and R 2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted C x to C 10 alkyl, substituted or unsubstituted to C 6 to C 15 aryl, and substituted and unsubstituted C x to C 10 alkoxy;
- R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , and R l ⁇ are each independently selected from a group consisting of hydrogen, substituted or unsubstituted C x to C 10 alkyl, substituted or unsubstituted C to C 10 alkoxy, substituted or unsubstituted C 6 to C 15 aryl, substituted or unsubstituted C 3 to C 10 cycloalkyl, and Si(R 12 ) 3 where R 12 is selected from the group consisting of C- L to C 10 alkyl, C 6 to C 15 aryl, or C 3 to C 10 cycloalkyl; and,
- R 7 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl, hydride, and Si(R 13 ) 3 where R 13 is selected from a group consisting of C ⁇ to C 10 alkyl, C 6 to C 15 aryl, and C 3 to C 10 cyclolalkyl .
- each pair of adjacent radicals on the cyclopentadienyl rings (e.g., R 4 and R 5 or R 10 and R 1X ) together may also form a cyclic group having 4 to 15 carbon atoms which in turn may be further substituted.
- M is a Group IV metal
- R and R 2 are each an electron withdrawing group
- R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , and R l are each selected from a group consisting of hydrogen, methyl, isopropyl, tert-butyl and trimethylsilyl .
- M is zirconium.
- the invention further includes a method for polymerizing olefins comprising the step of contacting an olefin with a catalyst of the type described above.
- the olefin may be a C 3 -C 10 ⁇ -olefin, and the olefin may be contacted with the catalyst in the presence of a solvent .
- the catalysts of the present invention are zwitterion ansa metallocenes that are referred to as ZAM catalysts.
- the inventive catalysts eliminates the need for a counterion like MAO while retaining or improving most of the various kinetic steps in olefin polymerization over prior art Ziegler-Natta catalysts .
- ZAM catalysts are of the general formula:
- M is selected from a group consisting of Group III, Group IV, Group V, and Group VI elements;
- E is boron or aluminum;
- R ⁇ and R 2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted C ⁇ to C 10 alkyl, substituted or unsubstituted to C 6 to C 15 aryl, and substituted and unsubstituted C to C 10 alkoxy;
- R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , and R ⁇ are each independently selected from a group consisting of hydrogen, substituted or unsubstituted C-_ to C 10 alkyl, substituted or unsubstituted C-_ to C 10 alkoxy, substituted or unsubstituted C 6 to C 15 aryl, substituted or unsubstituted C 3 to C 10 cycloalkyl, and Si(R 12 ) 3 where R 12 is selected from the group consisting of C to C 10 alkyl, C 6 to C 15 aryl, or C 3 to C 10 cycloalkyl; and, R 7 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl, hydride, and Si(R 13 ) 3 where R 13 is selected from a group consisting of C to C 10 alkyl, C 6 to C 15 aryl, and C 3 to C 10
- each pair of adjacent radicals on the cyclopentadienyl rings may also form a cyclic group having 4 to 15 carbon atoms which in turn may be further substituted.
- Examples of compounds wherein one or more pairs of adjacent radicals form cyclic ring include but are not limited to:
- R-_ and R 2 are each a group which increases the electrophilicity of the metal center.
- suitable groups include but are not limited to F, C 6 F 5 , and CF 3 .
- M is a Group IV metal
- R 3 3,' R 4 ,' R5e,' R ⁇ 6 6,' R ⁇ a 8#' R ⁇ 9' R 10' and R ⁇ l are each selected from a group consisting of hydrogen, methyl, isopropyl, tert-butyl and trimethylsilyl .
- M is zirconium.
- E is boron or aluminum
- R r and R 2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted C ⁇ to C 10 alkyl, substituted or unsubstituted to C 6 to C 15 aryl, and substituted and unsubstituted C to C 10 alkoxy;
- R 3 , R 4 , R 5 , and R 6 are each independently selected from a group consisting of hydrogen, substituted or unsubstituted C to C 10 alkyl, substituted or unsubstituted C-, ⁇ to C 10 alkoxy, substituted or unsubstituted C 6 to C 15 aryl, substituted or unsubstituted C 3 to C 10 cycloalkyl, and Si(R 9 ) 3 where R 9 is selected from the group consisting of C to C 10 alkyl, C 6 to C 15 aryl, or C 3 to C 10 cycloalkyl, wherein each pair of adjacent radicals together also may form a substituted or unsubstituted cyclic group having 4 to 15 carbons;
- R 7 is selected from a group consisting of hydrogen, substituted or unsubstituted C to C 10 alkyl, substituted or unsubstituted C x to C 10 alkoxy, substituted or unsubstituted C 6 to C 15 aryl, substituted or unsubstituted C 3 to C 10 cycloalkyl, and Si(R 10 ) 3 where R 10 is selected from the group consisting of C x to C 10 alkyl, C 6 to C 15 aryl, or C 3 to C 10 cycloalkyl; and,
- R 8 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl, hydride, and Si(R 11 ) 3 where R x is selected from a group consisting of C to C 10 alkyl, C 6 to C 15 aryl, and C 3 to C 10 cyclolalkyl .
- R 7 is tert-butyl or trimethyl-silyl .
- These compounds are variations of traditional metallocene catalysts and are generally referred to as mono-Cp "constrained- geometry catalysts" (or CGC) .
- CGC constrained- geometry catalysts
- the invention further includes a method for polymerizing olefins comprising the step of contacting an olefin with a catalyst of the types described above.
- the olefin may be a C 3 -C 10 ⁇ -olefin, and the olefin may be contacted with the catalyst in the presence of a solvent .
- the constrained-geometry embodiment of the present invention may be synthesized by known methods in the art, including but not limited to the protocol described by Organometallics, 9 : 866-869 (1990) which is incorporated herein by reference.
- the metallocene catalysts of the present invention may also be prepared by a variety of methods known in the art including the protocol described below. Although the protocol is for the preparation of (C 6 F 5 ) 2 B (C 5 H 4 ) 2 ZrCH 3 , persons skilled in the art would readily know how to adapt the protocol for the various inventive embodiments.
- DFT Density Functional Theory
- the Zr was described with the LACVP Hay Wadt effective core potential (ECP) to replace the core electrons [leaving the (4s) 2 (4p) 6 [ (4d) (5s) (5p)] 4 electrons to be described explicitly] and using the standard double zeta contraction.
- ECP effective core potential
- the results of the insertion reaction are summarized in Figure 1 which displays the energies along the reaction coordinates for ZAM I and control II.
- Figure 1 illustrates, the standard cationic metallocene binds ethylene exothermically by approximately 23 kcal/mol while the corresponding ZAM binds exothermically by about 16 kcal/mol.
- the insertion barrier for the cationic metallocene ranges from about 6-10 kcal/mol while ZAM has an insertion barrier of just less than 3 kcal/mol.
- the remaining energies of the ZAM catalyst were consistent with the energies of the cationic catalyst at the same level of theory.
- the energetics for the insertion reaction for ZAM I, ZAM III and control II are summarized in figure 2.
- the results for ZAM I and control II were calculated using DLDA-B3LYP and are consistent with the results using NLDA-GGAII.
Abstract
Des catalyseurs métallocènes à un seul composant pour la polymérisation d'α-oléfine sont décrits. Les catalyseurs métallocènes cationiques de l'art antérieur requièrent un co-catalyseur anionique séparé tel que l'aluminoxane de méthyl (MAO). Cependant, en raison de leur fonctionnalité 'intégrée' co-catalyseur anionique, les catalyseurs zwittérion ansa métallocène (ZAM) n'ont pas besoin d'un co-catalyseur anionique séparé.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU40532/97A AU4053297A (en) | 1996-08-09 | 1997-08-08 | Group iv zwitterion ansa metallocene (zam) catalysts for alpha-olefin polymerization |
| DE69723084T DE69723084T2 (de) | 1996-08-09 | 1997-08-08 | Katalysator auf basis eines zwitterionischen ansa metallocens der gruppe iv für die polymerisation von alpha-olefinen |
| EP97938137A EP0920455B1 (fr) | 1996-08-09 | 1997-08-08 | Catalyseurs zwitterion ansa metallocene du groupe iv pour la polymerisation d'alpha-olefines |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2439596P | 1996-08-09 | 1996-08-09 | |
| US60/024,395 | 1996-08-09 | ||
| US08/907,395 | 1997-08-07 | ||
| US90739598A | 1998-01-01 | 1998-01-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO1998006759A1 WO1998006759A1 (fr) | 1998-02-19 |
| WO1998006759A9 true WO1998006759A9 (fr) | 1998-06-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1997/013793 WO1998006759A1 (fr) | 1996-08-09 | 1997-08-08 | Catalyseurs zwitterion ansa metallocene du groupe iv pour la polymerisation d'alpha-olefines |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO1998006759A1 (fr) |
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| WO2020163079A1 (fr) | 2019-02-06 | 2020-08-13 | Exxonmobil Chemical Patents Inc. | Films et enveloppes de couche pour articles d'hygiène |
| WO2021126458A1 (fr) | 2019-12-17 | 2021-06-24 | Exxonmobil Chemical Patents Inc. | Films constitués de mélanges de polyéthylène, destinés à améliorer les performances d'étanchéité et les propriétés mécaniques |
| US12152135B2 (en) | 2020-03-12 | 2024-11-26 | Exxonmobil Chemical Patents Inc. | Films made of polyethylene blends for improved bending stiffness and high MD tear resistance |
| WO2022232760A1 (fr) | 2021-04-30 | 2022-11-03 | Exxonmobil Chemical Patents Inc. | Procédés pour la transition entre différents catalyseurs de polymérisation dans un réacteur de polymérisation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5470993A (en) * | 1993-06-24 | 1995-11-28 | The Dow Chemical Company | Titanium(II) or zirconium(II) complexes and addition polymerization catalysts therefrom |
| US5486632A (en) * | 1994-06-28 | 1996-01-23 | The Dow Chemical Company | Group 4 metal diene complexes and addition polymerization catalysts therefrom |
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- 1997-08-08 WO PCT/US1997/013793 patent/WO1998006759A1/fr active IP Right Grant
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