Olefin block copolymer and preparation method thereof

Patent metadata

Field	Value
Publication number	US-9527946-B2
Application number	US-201514795693-A
Country	US
Kind code	B2
Filing date	Jul 9, 2015
Priority date	Jan 21, 2011
Publication date	Dec 27, 2016
Grant date	Dec 27, 2016

Abstract

The present description relates to an olefin block copolymer having excellences in elasticity and heat resistance and its preparation method. The olefin block copolymer includes a plurality of blocks or segments, each of which includes an ethylene or propylene repeating unit and an α-olefin repeating unit at different weight fractions. The olefin block copolymer has a density of 0.85 to 0.92 g/cm 3 , and density X (g/cm 3 ) and TMA (Thermal Mechanical Analysis) value Y (° C.) satisfy a defined relationship.

First claim

What is claimed is:

1. A method for preparing an olefin block copolymer, comprising:
copolymerizing monomers comprising ethylene or propylene and α-olefin under conditions including a temperature of 140° C. or higher and a pressure of 50 bar of higher,
in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound having a ligand compound of Chemical Formula 1 coordinated with a Group IV transition metal, and a compound represented by the following Chemical Formula 2:

wherein m is an integer from 1 to 7;
R 1 is a C 4 -C 10 cycloalkyl group having at least one substituent selected from the group consisting of hydrogen, deuterium, halogen, nitrile, acetylene, amine, amide, ester, ketone, C 1 -C 20 alkyl, C 6 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 6 -C 20 aryl, silyl, C 7 -C 20 alkylaryl, C 7 -C 20 arylalkyl, and C 4 -C 20 heterocyclic; a C 3 -C 9 heterocyclic group having at least one substituent selected from the group consisting of hydrogen, deuterium, halogen, nitrile, acetylene, amine, amide, ester, ketone, C 1 -C 20 alkyl, C 6 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 6 -C 20 aryl, silyl, C 7 -C 20 alkylaryl, C 7 -C 20 arylalkyl, and C 4 -C 20 heterocyclic, and containing oxygen (O), nitrogen (N), or sulfur (S) as a hetero-atom; a C 6 -C 10 aryl group having at least one substituent selected from the group consisting of hydrogen, deuterium, halogen, nitrile, acetylene, amine, amide, ester, ketone, C 1 -C 20 alkyl, C 6 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 6 -C 20 aryl, silyl, C 7 -C 20 alkylaryl, C 7 -C 20 arylalkyl, and C 4 -C 20 heterocyclic; or a C 5 -C 10 hetero-aryl group having at least one substituent selected from the group consisting of hydrogen, deuterium, halogen, nitrile, acetylene, amine, amide, ester, ketone, C 1 -C 20 alkyl, C 6 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 6 -C 20 aryl, silyl, C 7 -C 20 alkylaryl, C 7 -C 20 arylalkyl, and C 4 -C 20 heterocyclic, and containing oxygen (O), nitrogen (N), or sulfur (S) as a hetero-atom, wherein when R 1 has at least two substituents, the adjacent two groups forms an aliphatic or aromatic condensed ring; and
R 2 s are the same or different from one another and independently selected from hydrogen, deuterium, halogen, nitrile, acetylene, amine, amide, ester, ketone, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 6 -C 20 aryl, C 4 -C 20 heterocyclic, C 1 -C 20 alkoxy, or C 6 -C 20 aryloxy, wherein at least two R 2 are linked to each other to form an aliphatic or aromatic ring,

wherein, R 1′ is R 2′ are independently hydrogen, C 1 -C 20 alkyl, C 6 -C 20 aryl, silyl, C 2 -C 20 alkenyl, C 7 -C 20 alkylaryl, C 7 -C 20 arylalkyl, or Group 14 metalloid radical having a hydrocarbyl substituent, wherein R 1′ and R 2′ are optionally linked to each other via an alkylidyne radical containing a C 1 -C 20 alkyl group or an aryl group to form a ring;
R 3′ s are independently hydrogen, halogen, C 1 -C 20 alkyl, C 6 -C 20 aryl, C 1 -C 20 alkoxy, C 6 -C 20 aryloxy, or amido, wherein at least two R 3′ s are optionally linked to each other to form an aliphatic or aromatic ring;
CY 1 is a substituted or unsubstituted aliphatic or aromatic ring;
M is a Group IV transition metal; and
Q 1 and Q 2 are independently halogen, C 1 -C 20 alkyl, C 6 -C 20 arylamido, C 2 -C 20 alkenyl, C 6 -C 20 aryl, C 7 -C 20 alkylaryl, C 7 -C 20 arylalkyl, or C 1 -C 20 alkylidene.

2. The method as claimed in claim 1 , wherein the catalyst composition further comprises at least one cocatalyst compound selected from the group consisting of compounds represented by the following Chemical Formulas 3, 4 and 5:
J(R 4′ ) 3   [Chemical Formula 3]

wherein J is aluminum (Al) or boron (B); and
R 4′ s are independently a halogen or a halogen-substituted or unsubstituted C 1 -C 20 hydrocarbyl radical,
[L-H] + [ZA 4 ] − or [L] + [ZA 4 ] −   [Chemical Formula 4]

wherein L is a neutral or cationic Lewis acid; H is hydrogen;
Z is a Group 13 element; and
A's are independently C 6 -C 20 aryl or C 1 -C 20 alkyl in which at least one hydrogen is substituted by a halogen, a C 1 -C 20 hydrocarbyl group, a C 1 -C 20 alkoxy group, or a phenoxy group,
—[Al(R 5′ )—O] a —  [Chemical Formula 5]

wherein R 5′ is a halogen or a halogen-substituted or unsubstituted C 1 -C 20 hydrocarbyl radical; and
a is an integer of 2 or greater.

3. The method as claimed in claim 1 , wherein the catalyst composition further comprises at least one polymerization aid selected from the group consisting of an aluminum compound containing a C 1 -C 12 hydrocarbyl substituent, a zinc compound containing a C 1 -C 12 hydrocarbyl substituent, and a gallium compound containing a C 1 -C 12 hydrocarbyl substituent.

4. The method as claimed in claim 1 , wherein the α-olefin comprises at least one α-olefin selected from the group consisting of 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-itocene.

5. The method as claimed in claim 1 , wherein the olefin block copolymer comprising a plurality of blocks or segments, each comprising an ethylene or propylene repeating unit and an α-olefin repeating unit at different weight fractions,
wherein the olefin block copolymer has a density of 0.85 to 0.92 g/cm 3 , and density X (g/cm 3 ) and TMA (Thermal Mechanical Analysis) value Y (° C.) satisfy the following Mathematical Formula 1:
Y≧ 1378.8 X− 1115  [Mathematical Formula 1]

wherein the olefin block copolymer has a melt index of 0.7 to 4.0 g/10 min under a load of 2.16 kg at 190° C. and a Shore hardness of 60 to 90, and
wherein the olefin block copolymer has a permanent recovery (after 300% elongation) of 20% to 60%.

6. The olefin block copolymer as claimed in claim 5 , wherein the density X (g/cm 3 ) and the TMA (Thermal Mechanical Analysis) value Y (° C.) satisfy the following Mathematical Formula 1a:
1378.8 X− 1076.3≧ Y≧ 1378.8 X− 1115  [Mathematical Formula 1a]

7. The method as claimed in claim 5 , wherein the TMA value is 70 to 140° C.

8. The method as claimed in claim 5 , wherein the olefin block copolymer comprises a hard segment comprising a first weight fraction of the α-olefin repeating unit and a soft segment comprising a second weight fraction of the α-olefin repeating unit,
wherein the second weight fraction is greater than the first weight fraction.

9. The method as claimed in claim 8 , wherein the weight fraction of the α-olefin repeating unit contained in the entire block copolymer has a value between the first and second weight fractions.

10. The method as claimed in claim 8 , wherein the olefin block copolymer comprises 10 to 90 wt. % of the hard segment and a remaining content of the soft segment.

11. The method as claimed in claim 8 , wherein the hard segment has a higher value than the soft segment in at least one property of the degree of crystallization, density, and melting temperature.

12. The method as claimed in claim 5 , wherein the olefin block copolymer comprises 30 to 90 wt. % of the ethylene or propylene repeating unit and a remaining content of the α-olefin repeating unit.

13. The method as claimed in claim 5 , wherein the olefin block copolymer has a melting temperature of 100 to 140° C.

14. The method as claimed in claim 5 , wherein the olefin b

Assignees

• Lg Chemical Ltd

Inventors

• Noh Kyung-Seop
• Lee Nan-Young
• Kim Won-Hee
• An Sang-Eun
• Jeon Sang-Jin
• Park Cheon-Il
• Lee Choong-Hoon

Classifications

• C08L23/08

  Copolymers of ethene (C08L23/16 takes precedence) · CPC title

• C08F295/00 Primary

  Macromolecular compounds obtained by polymerisation using successively different catalyst types without deactivating the intermediate polymer · CPC title

• C08F4/6592

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

• C08F4/64013

  NN · CPC title

• C08F297/08 Primary

  polymerising mono-olefins · CPC title