Polyolefin and preparation method thereof

Patent metadata

Field	Value
Publication number	US-9290593-B2
Application number	US-201314094365-A
Country	US
Kind code	B2
Filing date	Dec 2, 2013
Priority date	May 2, 2007
Publication date	Mar 22, 2016
Grant date	Mar 22, 2016

Abstract

A polyolefin has 1) a density in the range of 0.93 to 0.97 g/cm 3 , 2) a BOCD (Broad Orthogonal Co-monomer Distribution) index defined by a given equation in the range of 1 to 5, and 3) a molecular weight distribution (weight average molecular weight/number average molecular weight) in the range of 4 to 10. A supported hybrid metallocene catalyst comprises a first metallocene compound represented by a first given formulae, a second metallocene compound represented by one of three given formulae, and a support.

First claim

The invention claimed is:

1. A method of preparing a polyolefin using a supported hybrid catalyst in which at least two different transition metal catalyst compounds are supported in one support,
wherein the polyolefin has 1) a density in the range of 0.93 to 0.97 g/cm 3 , 2) a BOCD (Broad Orthogonal Co-monomer Distribution) index defined by the following Equation 1 in the range of 1 to 5, and 3) a molecular weight distribution (weight average molecular weight/number average molecular weight) in the range of 4 to 10:
BOCD Index=(Content of SCB at the high molecular weight side−Content of SCB at the low molecular weight side)/(Content of SCB at the low molecular weight side)  [Equation 1]

in the Equation 1, the “Content of SCB at the high molecular weight side” means the content of the SCB (the number of branches/1000 carbon atoms) included in a polymer chain having a molecular weight of Mw of the polyolefin or more and 1.3×Mw or less, and the “Content of SCB at the low molecular weight side” means the content of the SCB (the number of branches/1000 carbon atoms) included in a polymer chain having a molecular weight of 0.7×Mw of the polyolefin or more and less than Mw,
wherein a first transition metal catalyst compound, which is one of the transition metal catalyst compounds, is selected from the group consisting of [t-Bu-O—(CH 2 ) 6 —C 5 H 4 ] 2 ZrCl 2 and [t-Bu-O—(CH 2 ) 6 —C 5 H 4 ] 2 HfCl 2 , and a second transition metal catalyst compound, which is another type of the transition metal catalyst compounds, is a compound represented by the following Formula 4:

wherein
R7s are the same as or different from each other, and are each independently selected from hydrogen and a methyl radical; and
Q5 and Q6 are the same as or different from each other, and are each independently selected from a methyl radical and a chloride radical.

2. The method of preparing a polyolefin according to claim 1 , wherein the first transition metal catalyst compound is a catalyst used to obtain a polyolefin having a low weight average molecular weight in the range of 1,000 to 100,000, the second transition metal catalyst compound is a catalyst used to obtain a polyolefin having a high weight average molecular weight in the range of 10,000 to 1,000,000, and the weight average molecular weight of the polyolefin obtained by the second transition metal catalyst compound is higher than the weight average molecular weight of the polyolefin obtained by the first transition metal catalyst compound.

3. The method of preparing a polyolefin according to claim 1 , wherein the supported hybrid catalyst is manufactured by using a method which comprises:
a) bringing a supported transition metal catalyst in which at least one transition metal catalyst compound is supported into contact with a cocatalyst to manufacture an activated supported transition metal catalyst; and
b) additionally supporting one or more transition metal catalyst compounds that are different from the transition metal catalyst compound in the activated supported transition metal catalyst.

4. The method of preparing a polyolefin according to claim 3 , wherein the cocatalyst comprises a Group 13 metal of the periodic table, and a molar ratio of the Group 13 metal/Group 4 metal of the supported hybrid catalyst is in the range of 1 to 10,000.

5. The method of preparing a polyolefin according to claim 3 , wherein the cocatalyst is selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, tripentafluorophenyl boron, and tributylammoniumtetrapentafluorophenyl boron.

6. The method of preparing a polyolefin according to claim 1 , wherein the content of the Group 4 metal of the supported hybrid catalyst is in the range of 0.1 to 20% by weight.

7. The method of preparing a polyolefin according to claim 1 , wherein the molar ratio of the second transition metal catalyst compound to the first transition metal catalyst compound in the supported hybrid catalyst is in the range of 0.5 to 2.

8. The method of preparing a polyolefin according to claim 1 , wherein the supported hybrid catalyst further comprises the cocatalyst, and the molar ratio of the cocatalyst based on the metal included in the cocatalyst to the metal included in the first and second transition metal catalyst compounds is in the range of 1 to 10,000.

9. The method of preparing a polyolefin according to claim 1 , wherein the polyolefin is prepared in a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.

10. The method of preparing a polyolefin according to claim 1 , wherein a polymerization temperature is in the range of 25 to 500° C., and a polymerization pressure is in the range of 1 to 100 Kgf/cm 2 .

Assignees

• Lg Chemical Ltd

Inventors

• Cho Joon-Hee
• Lee Ki-Soo
• Han Yong-Gyu
• Hong Dae-Sik
• Kwon Heon-Yong
• Park Jong-Sang
• Kim Seon-Kyoung

Classifications

• C08F10/00 Primary

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F2500/10

  Short chain branches · CPC title

• C08F210/14 Primary

  Monomers containing five or more carbon atoms · CPC title

• C08F4/65927

  two cyclopentadienyl rings being mutually bridged · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title