Process for transitioning between incompatible catalysts
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-010/02
C08F-002/34
C08F-002/42
B01J-008/24
B01J-008/00
C08F-004/642
출원번호
US-0537997
(2015-12-22)
등록번호
US-9944727
(2018-04-17)
우선권정보
EP-14199694 (2014-12-22)
국제출원번호
PCT/EP2015/080946
(2015-12-22)
국제공개번호
WO2016/102548
(2016-06-30)
발명자
/ 주소
Banat, Yahya
Al-Humydi, Abdulaziz Hamad
Fellahi, Said
출원인 / 주소
SABIC GLOBAL TECHNOLOGIES B.V.
대리인 / 주소
Cantor Colburn LLP
인용정보
피인용 횟수 :
0인용 특허 :
44
초록▼
The invention relates to a process for transitioning from a first continuous polymerization reaction in a gas phase reactor conducted in the presence of a first catalyst to a second polymerization reaction conducted in the presence of a second catalyst in the gas phase reactor wherein the first and
The invention relates to a process for transitioning from a first continuous polymerization reaction in a gas phase reactor conducted in the presence of a first catalyst to a second polymerization reaction conducted in the presence of a second catalyst in the gas phase reactor wherein the first and second catalysts are incompatible, the process comprising: (a) discontinuing the introduction of the first catalyst into the gas phase reactor; (b) introducing an effective amount of cyclohexylamine into the reactor to at least partially deactivate the first catalyst; (c) introducing an organometallic compound into the reactor and reacting the organometallic compound with cyclohexylamine; (d) introducing a gas composition into the reactor for the second polymerization reaction and (e) introducing the second catalyst into the reactor.
대표청구항▼
1. A process for transitioning from a first continuous polymerization reaction in a gas phase reactor conducted in the presence of a first catalyst to a second polymerization reaction conducted in the presence of a second catalyst in the gas phase reactor wherein the first and second catalysts are i
1. A process for transitioning from a first continuous polymerization reaction in a gas phase reactor conducted in the presence of a first catalyst to a second polymerization reaction conducted in the presence of a second catalyst in the gas phase reactor wherein the first and second catalysts are incompatible, the process comprising: (a) discontinuing the introduction of the first catalyst into the gas phase reactor;(b) introducing an effective amount of cyclohexylamine into the reactor to at least partially deactivate the first catalyst;(c) introducing an organometallic compound into the reactor and reacting the organometallic compound with cyclohexylamine;(d) introducing a gas composition into the reactor for the second polymerization reaction and(e) introducing the second catalyst into the reactor. 2. The process according to claim 1, wherein the organometallic compound is a trialkylaluminum compound. 3. The process according to claim 1, further comprising the step (d2) after step (d) and before step (e), wherein step (d2) comprises introducing a reaction product of an aluminum compound of general formula (1) and an amine compound of general formula (2) wherein R1 is hydrogen or a branched or straight, substituted or unsubstituted hydrocarbon group having 1-30 carbon atoms,R2 and R3 are the same or different and selected from branched or straight, substituted or unsubstituted hydrocarbon groups having 1-30 carbon atoms andR4 is hydrogen or a functional group with at least one active hydrogenR5 is hydrogen or a branched, straight or cyclic, substituted or unsubstituted hydrocarbon group having 1-30 carbon atoms,R6 is a branched, straight or cyclic, substituted or unsubstituted hydrocarbon group having 1-30 carbon atoms is introduced into the reactor. 4. The process according to claim 3, wherein the compound (1) is tri-isobutylaluminum and the compound (2) is cyclohexylamine or octadecylamine or cyclohexylamine, octadecylamine, 2-ethylhexylamine, ethylhexylamine, bis(4-amino cyclohexyl)methane, hexamethylenediamine, 1,3-benzenedimethanamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 6-amino-1,3-dimethyluracil or a mixture thereof. 5. The process according to claim 1, wherein the first catalyst is a Ziegler-Natta catalyst and the second catalyst is a metallocene catalyst. 6. The process according to claim 1, wherein the second catalyst is a metallocene catalyst composition comprising a support containing a metallocene catalyst, a catalyst activator and an optional modifier. 7. The process according to claim 6, wherein the modifier is a reaction product of compound (1) being tri-isobutylaluminum and compound (2) being cyclohexylamine. 8. The process according to claim 6, wherein the metallocene catalyst is selected from the group consisting of: [ortho-bis(4-phenyl-2-indenyl)-benzene]zirconiumdichloride, [ortho-bis(5-phenyl-2-indenyl)-benzene]zirconiumdichloride, [ortho-bis(2-indenyl)benzene]zirconiumdichloride, [ortho-bis(2-indenyl)benzene]hafniumdichloride, [ortho-bis(1-methyl-2-indenyl)-benzene]zirconiumdichloride, [2.2′-(1.2-phenyldiyl)-1.1′-dimethylsilyl-bis(indene)]zirconiumdichloride, [2,2′-(1,2-phenyldiyl)-1, 1′-diphenylsilyl-bis(indene)]zirconiumdichloride, [2,2′-(1.2-phenyldiyl)-1.1′-(1.2-ethanediyl)-bis(indene)]zirconiumdichloride, [2.2′-bis(2-indenyl)biphenyl]zirconiumdichloride and [2,2′-bis(2-indenyl)biphenyl]hafniumdichloride. 9. The process according to claim 1, wherein the first catalyst is introduced from a first catalyst feeding system and the second catalyst is introduced from a second catalyst feeding system separate from the first catalyst feeding system. 10. The process according to claim 1, wherein the polymerization is conducted in a fluidized bed reactor. 11. The process according to claim 1, wherein the first continuous polymerization reaction is operated in a condensed mode in which 5-17.4 wt % of the gas composition entering the gas phase reactor is liquid or a supercondensed mode in which more than 17.4 wt % of the gas composition entering the gas phase reactor is liquid. 12. The process according to claim 1, wherein the gas phase reactor is a multi-zone reactor operable in condensed mode, which multi-zone reactor comprises a first zone, a second zone, a third zone, a fourth zone and a distribution plate, wherein the first zone is separated from the second zone by the distribution plate, wherein the multi-zone reactor is extended in the vertical direction,wherein the second zone of the multi-zone reactor is located above the first zone and wherein the third zone of the multi-zone reactor is located above the second zone, and wherein the fourth zone of the multi-zone reactor is located above the third zone,wherein the second zone contains an inner wall, wherein at least part of the inner wall of the second zone is either in the form of a gradually increasing inner diameter or a continuously opening cone, wherein the diameter or the opening increases in the vertical direction towards the top of the multi-zone reactor,wherein the third zone contains an inner wall, wherein at least part of the inner wall of the third zone is either in the form of a gradually increasing inner diameter or a continuously opening cone, wherein the diameter or the opening increases in the vertical direction towards the top of the multi-zone reactor, andwherein the largest diameter of the inner wall of the third zone is larger than the largest diameter of the inner wall of the second zone. 13. The process according to claim 1, wherein a reversible catalyst killer is introduced to render the first catalyst inactive. 14. The process according to claim 1, wherein the organometallic compound is triethylaluminum, trimethylaluminum, tri-isobutylaluminum, or tri-n-hexylaluminum. 15. The process according to claim 1, wherein the organometallic compound is tri-isobutylaluminum. 16. The process according to claim 6, wherein the optional modifier is present and is [A] a reaction product of an aluminum compound of general formula (1) and an amine compound of general formula (2) wherein R1 is hydrogen or a branched or straight, substituted or unsubstituted hydrocarbon group having 1-30 carbon atoms,R2 and R3 are the same or different and are selected from branched or straight, substituted or unsubstituted hydrocarbon groups having 1-30 carbon atoms,R4 is hydrogen or a functional group with at least one active hydrogen,R5 is hydrogen or a branched, straight or cyclic, substituted or unsubstituted hydrocarbon group having 1-30 carbon atoms, andR6 is a branched, straight or cyclic, substituted or unsubstituted hydrocarbon group having 1-30 carbon atoms, or[B] an amine compound of general formula (3) where R7 is hydrogen or a linear or branched alkyl group of from 1 to 50 carbon atoms,R8 is a hydroxy group of a (CH2)X radical andx is an integer from 1 to 50. 17. The process according to claim 7, wherein the metallocene catalyst is selected from the group consisting of: [ortho-bis(4-phenyl-2-indenyl)-benzene]zirconiumdichloride, [ortho-bis(5-phenyl-2-indenyl)-benzene]zirconiumdichloride, [ortho-bis(2-indenyl)benzene]zirconiumdichloride, [ortho-bis(2-indenyl)benzene]hafniumdichloride, [ortho-bis(1-methyl-2-indenyl)-benzene]zirconiumdichloride, [2.2′-(1.2-phenyldiyl)-1.1′-dimethylsilyl-bis(indene)]zirconiumdichloride, [2,2′-(1,2-phenyldiyl)-1,1′-diphenylsilyl-bis(indene)]zirconiumdichloride, [2,2′-(1.2-phenyldiyl)-1.1′-(1.2-ethanediyl)-bis(indene)]zirconiumdichloride, [2.2′-bis(2-indenyl)biphenyl]zirconiumdichloride and [2,2′-bis(2-indenyl)biphenyl]hafniumdichloride. 18. The process according to claim 13, wherein the reversible catalyst killer is CO. 19. The process according to claim 17, wherein the first catalyst is introduced from a first catalyst feeding system and the second catalyst is introduced from a second catalyst feeding system separate from the first catalyst feeding system;wherein the polymerization is conducted in a fluidized bed reactor; andwherein the first continuous polymerization reaction is operated in a condensed mode in which 5-17.4 wt % of the gas composition entering the gas phase reactor is liquid or a supercondensed mode in which more than 17.4 wt % of the gas composition entering the gas phase reactor is liquid. 20. The process according to claim 19, wherein the gas phase reactor is a multi-zone reactor operable in condensed mode, which multi-zone reactor comprises a first zone, a second zone, a third zone, a fourth zone and a distribution plate, wherein the first zone is separated from the second zone by the distribution plate, wherein the multi-zone reactor is extended in the vertical direction,wherein the second zone of the multi-zone reactor is located above the first zone and wherein the third zone of the multi-zone reactor is located above the second zone, and wherein the fourth zone of the multi-zone reactor is located above the third zone,wherein the second zone contains an inner wall, wherein at least part of the inner wall of the second zone is either in the form of a gradually increasing inner diameter or a continuously opening cone, wherein the diameter or the opening increases in the vertical direction towards the top of the multi-zone reactor,wherein the third zone contains an inner wall, wherein at least part of the inner wall of the third zone is either in the form of a gradually increasing inner diameter or a continuously opening cone, wherein the diameter or the opening increases in the vertical direction towards the top of the multi-zone reactor, andwherein the largest diameter of the inner wall of the third zone is larger than the largest diameter of the inner wall of the second zone.
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