Supported hybrid catalyst and method for preparing olefin polymer using the same

Patent metadata

Field	Value
Publication number	US-2018194873-A1
Application number	US-201715742001-A
Country	US
Kind code	A1
Filing date	Jan 26, 2017
Priority date	Jan 27, 2016
Publication date	Jul 12, 2018
Grant date	—

Abstract

The present invention relates to a supported hybrid catalyst and a method for preparing olefin polymer using the same. Using the supported hybrid catalyst, olefin polymer that maintains excellent mechanical strength of olefin polymer polymerized with the existing metallocene catalyst, but exhibits remarkably improved processibility compared to the existing olefin polymer, can be provided.

First claim

1 . A supported hybrid catalyst comprising a carrier; a transition metal compound represented by the following Chemical Formula 1, which is supported on the carrier; and one or more kinds of transition metal compounds represented by the following Chemical Formula 2, which are supported on the carrier:

in the Chemical Formulas 1 and 2, M 1 and M 2 are identical to or different from each other, and each independently, Ti, Zr or Hf,
X 1 , X 2 , X 3 and X 4 are identical to or different from each other, and each independently, halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C1-20 alkyl group, a C1-20 alkoxy group, a C2-20 alkoxyalkyl group, a C1-20 silyl group, a C2-20 alkenyl group, a C6-20 aryl group, a C1-20 sulfonate group, or a C1-20 sulfone group,
T 1 is C, Si, Ge, Sn or Pb,
T 2 is a C1-5 alkylene group, a C2-10 alkylidene group, or T 3 (Q 3 )(Q 4 ),
T 3 is C, Si, Ge, Sn or Pb,
Q 1 , Q 2 , Q 3 and Q 4 are identical to or different from each other, and each independently, hydrogen, halogen, a C1-20 alkyl group, a C2-20 heterocycloalkyl group, a C1-20 alkoxyl group, a C2-20 alkoxyalkyl group, a C1-20 carboxylate, a C2-20 alkenyl group, a C6-20 aryl group, or a C5-20 heteroaryl group,
R 1 to R 6 are identical to or different from each other, and each independently, hydrogen, a C1-20 alkyl group, a C1-20 alkoxyl group, a C2-20 alkoxyalkyl group, a C1-20 silyl group, a C1-20 silylalkyl group, a C1-20 silyloxyalkyl group, a C2-20 alkenyl group, or a C6-20 aryl group,
R 7 to R 14 are identical to or different from each other, and each independently, hydrogen, a C1-20 alkyl group, a C1-20 alkoxyl group, a C2-20 alkoxyalkyl group, a C1-20 silyl group, a C1-20 silylalkyl group, a C1-20 silyloxyalkyl group, a C2-20 alkenyl group, or a C6-20 aryl group, or one or more neighboring pairs of R 7 to R 14 are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring,
Cp1 and Cp2 are identical to or different from each other, and each independently, —NR 15 —, an aromatic ring selected from a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group or an indenoindolyl group, or the above aromatic ring of which one or more hydrogen atoms are independently substituted with a C1-20 alkyl group, a C1-20 alkoxy group, a C2-20 alkoxyalkyl group, a C1-20 silyl group, a C2-20 silylalkyl group, or a C6-20 aryl group, and
R 15 is a C1-20 alkyl group.

2 . The supported hybrid catalyst according to claim 1 , wherein R 1 to R 4 are each independently, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, or a C2-20 alkenyl group.

3 . The supported hybrid catalyst according to claim 1 , wherein R 5 and R 6 are each independently, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, or a C2-20 alkenyl group.

4 . The supported hybrid catalyst according to claim 1 , wherein R 7 to R 14 are each independently, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, or a C2-20 alkenyl group, or one or more neighboring pairs of R 7 to R 14 are connected to each other to form a substituted or unsubstituted aliphatic ring.

5 . The supported hybrid catalyst according to claim 1 , wherein Q 1 and Q 2 are each independently, a C1-20 alkyl group, or a C6-20 aryl group.

6 . The supported hybrid catalyst according to claim 1 , wherein X 1 to X 4 are each independently, halogen, a C1-20 alkyl group, or a C1-20 alkoxyl group.

7 . The supported hybrid catalyst according to claim 1 , wherein T 2 is an ethylene group, an n-propylene group, an iso-propylene group, an ethylidene group, a 1-propylidene group, 2-propylidene group, or T 3 (Q 3 )(Q 4 ); T 3 is Si; and Q 3 and Q 4 are identical to or different from each other, and each independently, a C1-20 alkyl group, a C1-20 alkoxy group, or a C2-20 alkoxyalkyl group.

8 . The supported hybrid catalyst according to claim 1 , wherein Cp1 and Cp2 are identical to or different from each other, and each independently, —N(tert-butyl)-, a cyclopentadienyl group, a tetramethylcyclopentadienyl group, a tert-buthoxyhexylcyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a 5,10-dihydroindeno[1,2-b]indolyl group, or a 5,8-dimethyl-5,10-dihydroindeno[1,2-b]indolyl group.

9 . The supported hybrid catalyst according to claim 1 , wherein the transition metal compound represented by the Chemical Formula 1 is a compound represented by the following Chemical Formula 3 or 4:

in the Chemical Formulas 3 and 4, R 16 and R 17 are identical to or different from each other, and each independently, hydrogen, a C1-20 alkyl group, a C1-20 alkoxy group, a C2-20 alkoxyalkyl group, a C1-20 alkylsilyl group, a C1-20 silylalkyl group, a C1-20 alkoxysilyl group, a C1-20 silyloxyalkyl group, a C2-20 alkenyl group, a C6-20 aryl group, a C7-20 alkylaryl group, or a C7-20 arylalkyl group, and
l is an integer of 0 to 5.

10 . The supported hybrid catalyst according to claim 1 , wherein the transition metal compound represented by the Chemical Formula 2 is dimethylsilylene(tetramethylcyclopentadienyl)(9H-fluorene-9-yl)zirconium dichloride.

11 . The supported hybrid catalyst according to claim 1 , further comprising one or more kinds of cocatalysts selected from the group consisting of the compounds represented by the following Chemical Formulas 5 to 7:
R 19 —[Al(R 18 )—O] n —R 20   [Chemical Formula 5]
in the Chemical Formula 5, R 18 , R 19 and R 20 are each independently, hydrogen, halogen, a C1-20 hydrocarbyl group, or a C1-20 hydrocarbyl group substituted with halogen, and n is an integer of 2 or more,
D(R 21 ) 3   [Chemical Formula 6]

in the Chemical Formula 6, D is aluminium or boron, R 21 's are each independently, halogen, a C1-20 hydrocarbyl group, or a C1-20 hydrocarbyl group substituted with halogen,
[L-H] + [Z(A) 4 ] − or [L] + [Z(A) 4 ] −   [Chemical Formula 7]

in the Chemical Formula 7, L is neutral or cationic Lewis base, H is a hydrogen atom, Z is a Group 13 atom, A's are each independently, a C1-20 hydrocarbyl group; a C1-20 hydrocarbyloxy group; or a C1-20 hydrocarbyl group or a C1-20 hydrocarbyloxy group of which one or more hydrogen atoms are substituted with halogen, a C1-20 hydrocarbyloxy group or a C1-20 hydrocarbylsilyl group.

12 . The supported hybrid catalyst according to claim 1 , wherein the carrier is silica, alumina, magnesia or a mixture thereof.

13 . The supported hybrid catalyst according to claim 1 , wherein the transition metal compound represented by the Chemical Formula 1 and the transition metal compound represented by the Chemical Formula 2 are included in the weight ratio of 10:0.01 to 10:50.

14 . A method for preparing olefin polymer comprising the step of polymerizing olefin monomers in the presence of the supported hybrid catalyst of claim 1 .

15 . The method according to claim 14 , wherein the olefin monomer includes one or more kinds selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidenenorbordene, phenylnorbordene, vinylnorbordene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divin

Assignees

• Lg Chemical Ltd

Inventors

• Kwon Hyun Jee
• Kwon Heon Yong
• Hong Dae Sik
• Kim Dae Hwan
• Lee Sung Min
• Shin Eun Young
• Park Sung Ho
• You Young Suk
• Lee Jin Young

Classifications

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08F4/65916

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title

• C08L23/0815

  with aliphatic 1-olefins containing one carbon-to-carbon double bond · CPC title

• C08F4/6592

  containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring · CPC title

• C08F110/02 Primary

  Ethene · CPC title