[미국특허]
Methods for controlling molecular weight and molecular weight distribution
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C08F-004/6592
C08F-004/642
C08F-110/02
C08F-210/16
출원번호
US-0690364
(2017-08-30)
등록번호
US-10005865
(2018-06-26)
발명자
/ 주소
Cruz, Carlos A.
Barr, Jared L.
출원인 / 주소
Chevron Phillips Chemical Company LP
대리인 / 주소
Merchant & Gould P.C.
인용정보
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0인용 특허 :
59
초록▼
Methods for controlling or adjusting the molecular weight and molecular weight distribution of an olefin polymer, such as an ethylene polymer, using an alkylaluminum compound are disclosed. In addition to the alkylaluminum compound, the catalyst systems contain a half-metallocene titanium phosphinim
Methods for controlling or adjusting the molecular weight and molecular weight distribution of an olefin polymer, such as an ethylene polymer, using an alkylaluminum compound are disclosed. In addition to the alkylaluminum compound, the catalyst systems contain a half-metallocene titanium phosphinimide compound and an activator.
대표청구항▼
1. An olefin polymerization process, the process comprising: (i) contacting a half-metallocene titanium phosphinimide compound and an alkylaluminum compound for a first period of time to form a precontacted mixture;(ii) contacting the precontacted mixture with an activator and an optional co-catalys
1. An olefin polymerization process, the process comprising: (i) contacting a half-metallocene titanium phosphinimide compound and an alkylaluminum compound for a first period of time to form a precontacted mixture;(ii) contacting the precontacted mixture with an activator and an optional co-catalyst for a second period of time to form a catalyst composition; and(iii) contacting the catalyst composition with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer; wherein:a Mw of the olefin polymer produced by the process is greater than the Mw of an olefin polymer produced under the same polymerization conditions using a catalyst system obtained by simultaneously combining the half-metallocene titanium phosphinimide compound, the alkylaluminum compound, the activator, and the optional co-catalyst. 2. The process of claim 1, wherein the alkylaluminum compound comprises trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, or any combination thereof. 3. The process of claim 1, wherein the half-metallocene titanium phosphinimide compound has the formula: (B); wherein: X1 and X2 independently are a halide;R1, R2, and R3 independently are H or a halide, C1 to C36 hydrocarbyl group, C1 to C36 halogenated hydrocarbyl group, C1 to C36 hydrocarboxy group, or C1 to C36 hydrocarbylsilyl group; andCp is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group. 4. The process of claim 3, wherein: X1 and X2 are Cl;R1, R2, and R3 independently are H or C1 to C18 hydrocarbyl group; andCp is an unsubstituted cyclopentadienyl or indenyl group. 5. The process of claim 1, wherein the first period of time is in a range from about 30 minutes to about 36 hours. 6. The process of claim 1, wherein the Mw of the olefin polymer produced by the process is at least about 25% greater than the Mw of the olefin polymer produced under the same polymerization conditions using a catalyst system obtained by simultaneously combining the half-metallocene titanium phosphinimide compound, the alkylaluminum compound, the activator, and the optional co-catalyst. 7. The process of claim 1, wherein the molar ratio of the alkylaluminum compound to the half-metallocene titanium phosphinimide compound in step (i) is in a range from about 1:1 to about 5:1. 8. The process of claim 1, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof. 9. The process of claim 1, wherein the activator comprises an activator-support, the activator-support comprising a solid oxide treated with an electron-withdrawing anion. 10. The process of claim 1, wherein: the polymerization reactor system comprises a slurry reactor, gas-phase reactor, solution reactor, or a combination thereof, andthe catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof. 11. The process of claim 10, wherein: the precontacted mixture is contacted with the activator and an organoaluminum co-catalyst in step (ii); andthe activator comprises a fluorided solid oxide and/or a sulfated solid oxide. 12. The process of claim 1, wherein: the olefin polymer comprises an ethylene homopolymer and/or an ethylene/α-olefin copolymer;the activator comprises an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof; andthe Mw of the olefin polymer produced by the process is at least about 25% greater than the Mw of the olefin polymer produced under the same polymerization conditions using a catalyst system obtained by simultaneously combining the half-metallocene titanium phosphinimide compound, the alkylaluminum compound, the activator, and the optional co-catalyst. 13. A process for producing an ethylene polymer with a target ratio of Mw/Mn, the process comprising: (a) selecting an alkylaluminum compound based on a solubility parameter of the alkylaluminum compound; and(b) contacting a catalyst composition with ethylene and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce the ethylene polymer with the target ratio of Mw/Mn;wherein the catalyst composition comprises a half-metallocene titanium phosphinimide compound, an activator, and the alkylaluminum compound. 14. The process of claim 13, wherein: the alkylaluminum compound comprises trimethylaluminum, triethylaluminum, or a combination thereof; andthe target ratio of Mw/Mn is in a range from about 2.5 to about 6. 15. The process of claim 13, wherein: Mw/Mn increases as the solubility parameter decreases; andthe polymerization reactor system comprises a slurry reactor, gas-phase reactor, solution reactor, or a combination thereof. 16. The process of claim 13, wherein the ethylene polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, or any combination thereof;the activator comprises an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof; andthe half-metallocene titanium phosphinimide compound has the formula: (B); wherein: X1 and X2 independently are a halide;R1, R2, and R3 independently are H or a halide, C1 to C36 hydrocarbyl group, C1 to C36 halogenated hydrocarbyl group, C1 to C36 hydrocarboxy group, or C1 to C36 hydrocarbylsilyl group; andCp is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group. 17. A process for controlling a ratio of Mw/Mn of an ethylene polymer, the process comprising: (A) contacting a catalyst composition with ethylene and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce the ethylene polymer,wherein the catalyst composition comprises a half-metallocene titanium phosphinimide compound, an activator, and an alkylaluminum compound; and(B) adjusting a solubility parameter of the alkylaluminum compound to control the ratio of Mw/Mn of the ethylene polymer. 18. The process of claim 17, wherein Mw/Mn increases as the solubility parameter decreases. 19. The process of claim 17, wherein: the alkylaluminum compound comprises trimethylaluminum, triethylaluminum, or a combination thereof; andthe ratio of Mw/Mn of the ethylene polymer is in a range from about 2.5 to about 6. 20. The process of claim 17, wherein: the alkylaluminum compound comprises triisobutylaluminum,trioctylaluminum, or a combination thereof; andthe ratio of Mw/Mn of the ethylene polymer is in a range from about 6.5 to about 15.
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