Elastic diene terpolymer and preparation method thereof

Patent metadata

Field	Value
Publication number	US-9650460-B2
Application number	US-201414442674-A
Country	US
Kind code	B2
Filing date	Jun 30, 2014
Priority date	Jun 28, 2013
Publication date	May 16, 2017
Grant date	May 16, 2017

Abstract

The present invention relates to a long-chain branched elastic terpolymer capable of satisfying excellent processability and elasticity (flexibility) at the same time, which is obtained in the presence of a Group IV transition metal catalyst, and a preparation method thereof. The elastic terpolymer is a copolymer of ethylene, an alpha-olefin having 3 to 20 carbon atoms, and a diene, wherein
i) its weight average molecular weight measured by GPC is 100,000 to 500,000, and ii) x which is the ethylene content (% by weight) and y which is the density value (g/cm 3 ) of the copolymer measured when the ethylene content is X satisfy a relationship of 0.0000175214x(x−75.65420571)+0.875≦y≦0.0000175214x(x−75.65420571)+0.881.

First claim

The invention claimed is:

1. An elastic terpolymer, wherein the elastic terpolymer is a copolymer of ethylene, an alpha-olefin having 3 to 20 carbon atoms, and a diene, obtained in the presence of a Group IV transition metal catalyst, wherein
i) its weight average molecular weight measured by GPC is 100,000 to 500,000, and
ii) x which is an ethylene content (% by weight) and y which is a density value (g/cm 3 ) of the copolymer measured when the ethylene content is X satisfy a relationship of 0.0000175214x(x−75.65420571)+0.875≦y≦0.0000175214x(x−75.65420571)+0.881.

2. The elastic terpolymer of claim 1 , wherein an LCB Index which is a ratio of 1 st harmonics of storage modulus to 5 th harmonics of storage modulus measured at 125° C. using a rubber process analyzer according to a LAOS (Large Angles of Oscillation and high Strains) method has a positive value.

3. The elastic terpolymer of claim 2 , wherein the LCB Index is more than 0 and 5 or less.

4. The elastic terpolymer of claim 1 , wherein Re*Rc is less than 1, in which Re*Rc is a product of a reactivity ratio Re representing the distribution of ethylene in the copolymer and a reactivity ratio Rc representing the distribution of alpha-olefin in the copolymer, and
Re=k11/k12 and Rc=k22/k21, wherein k11 is a growth reaction rate constant when ethylene binds next to ethylene in the copolymer chain, k12 is a growth reaction rate constant when alpha-olefin binds next to ethylene in the copolymer chain, k21 is a growth reaction rate constant when ethylene binds next to alpha-olefin in the copolymer chain, and k22 is a growth reaction rate constant when alpha-olefin binds next to alpha-olefin in the copolymer chain.

5. The elastic terpolymer of claim 4 , wherein, Re*Rc is 0.60 to 0.99.

6. The elastic terpolymer of claim 1 , wherein the copolymer of ethylene, the alpha-olefin having 3 to 20 carbon atoms, and the diene is a copolymer of 40 to 80% by weight of ethylene, 15 to 55% by weight of the alpha-olefin having 3 to 20 carbon atoms, and 4 to 6% by weight of the diene.

7. The elastic terpolymer of claim 1 , wherein the elastic terpolymer has a density of 0.840 to 0.895 g/cm 3 .

8. The elastic terpolymer of claim 1 , wherein the elastic terpolymer has Mooney viscosity (1+4{circle around (a)}125° C.) of 5 to 180.

9. The elastic terpolymer of claim 1 , wherein the elastic terpolymer has a molecular weight distribution of 2 to 4.

10. The elastic terpolymer of claim 1 , wherein the alpha-olefin is one or more selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, and the diene is one or more selected from the group consisting of 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, and 4-hexadiene.

11. A method for preparing the elastic terpolymer of claim 1 , comprising the step of continuously feeding a monomer composition containing 40 to 80% by weight of ethylene, 15 to 55% by weight of the alpha-olefin having 3 to 20 carbon atoms, and 4 to 6% by weight of the diene to a reactor to perform copolymerization in the presence of a catalytic composition including a first transition metal compound represented by the following Chemical Formula 1 and a second transition metal compound represented by the following Chemical Formula 2:

wherein R 1 to R 13 are the same as or different from each other, and are each independently hydrogen, an alkyl radical having 1 to 20 carbon atoms, an alkenyl radical having 2 to 20 carbon atoms, an aryl radical having 6 to 20 carbon atoms, a silyl radical, an alkylaryl radical having 7 to 20 carbon atoms, an arylalkyl radical having 7 to 20 carbon atoms, or a hydrocarbyl-substituted metalloid radical of a Group IV metal; of R 1 to R 13 , two different neighboring groups are connected to each other by an alkylidine radical containing an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms to form an aliphatic or aromatic ring;
M is a Group IV transition metal; and
Q 1 and Q 2 are the same as or different from each other, and are each independently a halogen radical, an alkyl radical having 1 to 20 carbon atoms, an alkenyl radical having 2 to 20 carbon atoms, an aryl radical having 6 to 20 carbon atoms, an alkylaryl radical having 7 to 20 carbon atoms, an arylalkyl radical having 7 to 20 carbon atoms, an alkylamido radical having 1 to 20 carbon atoms, an arylamido radical having 6 to 20 carbon atoms, or an alkylidene radical having 1 to 20 carbon atoms.

12. The method of claim 11 , wherein the first transition metal compound is one or more selected from the group consisting of the following compounds:

wherein R 2 and R 3 are the same as or different from each other and are each independently hydrogen or a methyl radical, M is a Group IV transition metal, and Q 1 and Q 2 are the same as or different from each other and are each independently a methyl radical, a dimethylimido radical, or a chlorine radical.

13. The method of claim 11 , wherein the second transition metal compound is one or more selected from the group consisting of the following compounds:

wherein R 2 and R 3 are the same as or different from each other and are each independently hydrogen or a methyl radical, M is a Group IV transition metal, and Q 1 and Q 2 are the same as or different from each other and are each independently a methyl radical, a dimethylimido radical, or a chlorine radical.

14. The method of claim 11 , wherein the catalytic composition further includes one or more co-catalytic compounds selected from the group consisting of the following Chemical Formula 3, Chemical Formula 4, and Chemical Formula 5:
—[Al(R)—O] n —  [Chemical Formula 3]

wherein R's are the same as or different from each other and are each independently a halogen, a hydrocarbon having 1 to 20 carbon atoms, or a halogen-substituted hydrocarbon having 1 to 20 carbon atoms, and n is an integer of 2 or more;
D(R) 3   [Chemical Formula 4]

wherein R is the same as defined in Chemical Formula 3, and D is aluminum or boron; and
[L-H] + [ZA 4 ] − or [L] + [ZA 4 ] −   [Chemical Formula 5]

wherein L is a neutral or cationic Lewis acid, H is a hydrogen atom, Z is an element of Group 13, and A's are the same as or different from each other and are each independently an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, in which one or more hydrogen atoms are unsubstituted or substituted with a halogen, a hydrocarbon having 1 to 20 carbon atoms, an alkoxy, or a phenoxy.

15. The method of claim 11 , wherein the alpha-olefin is one or more selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, and the diene is one or more selected from the group consisting of 5-ethylidene-2-norbornene, 5-methylene-2-norbomene, and 4-hexadiene.

16. The method of claim 11 , wherein copolymerization is performed while continuously feeding the monomer composition, the first and second transition metal compounds, and the co-catalyst in a solution state to a reactor.

17. The method of claim 16 , wherein the copolymerization step is continuously performed while continuously discharging the copolymerized elastic terpolymer from the reactor.

18. The method of claim 11 , wherein the copolymer

Assignees

• Lg Chemical Ltd

Inventors

• Park Sung Ho
• Yoon Sung Cheol
• Kim Sun Keun
• Ko Jun Seok
• Park Sang Eun
• Choi Soo Young

Classifications

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• C08F4/65904

  in combination with another component of C08F4/64 · CPC title

• C08L23/16

  Ethylene-propylene or ethylene-propylene-diene copolymers · CPC title

• C08F236/02 Primary

  the radical having only two carbon-to-carbon double bonds · CPC title

• C08F210/18 Primary

  with non-conjugated dienes, e.g. EPT rubbers · CPC title