Hybrid supported metallocene catalyst and process for preparing polyethylene copolymer using the same
The present disclosure provides a hybrid supported metallocene catalyst useful for preparing a polyethylene copolymer capable of producing an mLLDPE shrink film having excellent shrinkage and processability with excellent mechanical properties, and a process for preparing a polyethylene copolymer using the same. The hybrid supported metallocene catalyst comprises at least one first metallocene compound selected from compounds represented by the following Chemical Formula 1 and at least one second metallocene compound selected from compounds represented by the following Chemical Formula 2: wherein the variables are described herein.
1. A hybrid supported metallocene catalyst, comprising at least one first metallocene compound selected from compounds represented by the following Chemical Formula 1; at least one second metallocene compound selected from compounds represented by the following Chemical Formula 2; and a support on which the first and the second metallocene compounds are supported:
in Chemical Formula 1,
M 1 is a Group 4 transition metal;
A is carbon (C), silicon (Si), or germanium (Ge);
X 1 and X 2 are the same as or different from each other, and are each independently halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH 3 , a C1 to C30 hydrocarbyl (oxy) silyl group, a C1 to C30 sulfonate group, or a C1 to C30 sulfone group;
R 1 and R 3 to R 10 are the same as or different from each other, and are each independently hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, or a C2 to C30 hydrocarbyloxyhydrocarbyl group;
R 2 is hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, a C1 to C20 hydrocarbyl (oxy) silyl group, or a Cl to C20 silylhydrocarbyl group; and
Q 1 and Q 2 are the same as or different from each other, and are each independently a C1 to C30 hydrocarbyl group, or a C1 to C30 hydrocarbyloxy group;
in Chemical Formula 2,
M 2 is a Group 4 transition metal;
X 3 and X 4 are the same as or different from each other, and are each independently halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH 3 , a C1 to C30 hydrocarbyl (oxy) silyl group, a Cl to C30 sulfonate group, or a C1 to C30 sulfone group;
Z is —O—, —S—, —NR a —, or —PR a —;
R a is hydrogen, a C1 to C20 hydrocarbyl group, a C1 to C20 hydrocarbyl (oxy) silyl group, or a C1 to C20 silylhydrocarbyl group;
T is
T 1 is C, Si, Ge, Sn, or Pb;
Q 3 is hydrogen, a C1 to C30 hydrocarbyl group, a C1 to C30 hydrocarbyloxy group, a C2 to C30 hydrocarbyloxyhydrocarbyl group, —SiH 3 , a C1 to C30 hydrocarbyl (oxy) silyl group, a C1 to C30 hydrocarbyl group substituted with halogen, or —NR b R c ;
Q 4 is a C2 to C30 hydrocarbyloxyhydrocarbyl group;
R b and R c are each independently hydrogen, or a C1 to C30 hydrocarbyl group, or R b and R c are connected with each other, and together with N to which they are attached to form an aliphatic or aromatic ring; and
C 1 is any one of ligands represented by the following Chemical Formulae 2a to 2d,
in Chemical Formulae 2a to 2d,
Y is O, or S,
R 11 to R 16 are the same as or different from each other, and are each independently hydrogen, a C1 to C30 hydrocarbyl group, or a C1 to C30 hydrocarbyloxy group;
represents a site of binding to T, and
represents a site of binding to M 2 .
2. The hybrid supported metallocene catalyst of claim 1 ,
wherein the first metallocene compound is represented by the following Chemical Formula 1-1:
in Chemical Formula 1-1, M 1 , X 1 , X 2 , R 2 , R 7 to R 10 , A, Q 1 , and Q 2 are the same as defined in claim 1 .
3. The hybrid supported metallocene catalyst of claim 1 ,
wherein M 1 is titanium (Ti), zirconium (Zr) or hafnium (Hf),
A is silicon (Si), and
each of X 1 and X 2 is independently halogen.
4. The hybrid supported metallocene catalyst of claim 1 ,
wherein each of R 1 and R 3 to R 6 is hydrogen, and
R 2 is hydrogen, a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C2 to C10 alkenyl group, a C6 to C12 aryl group, a C7 to C14 arylalkyl group, a C7 to C14 alkylaryl group, a C1 to 10 alkylsilyl group, a C1 to C10 silylalkyl group, or a C2 to C12 alkylsilylalkylene group.
5. The hybrid supported metallocene catalyst of claim 1 ,
wherein each of R 1 and R 3 to R 6 is hydrogen, and
R 2 is hydrogen, methyl, ethyl, propyl, butyl, butenyl, trimethylsilylmethyl, or phenyl.
6. The hybrid supported metallocene catalyst of claim 1 ,
wherein each of R 7 to R 10 is independently a C1 to C20 alkyl group.
7. The hybrid supported metallocene catalyst of claim 1 ,
wherein each of Q 1 and Q 2 is independently a C1 to C20 alkyl group, or a C6 to C12 aryl group.
8. The hybrid supported metallocene catalyst of claim 1 ,
wherein the first metallocene compound is represented by one of the following structural formulae:
9. The hybrid supported metallocene catalyst of claim 1 ,
wherein Z is —NR a —, and R a is a C1 to C10 hydrocarbyl group.
10. The hybrid supported metallocene catalyst of claim 1 ,
where T is
T 1 is carbon (C), or silicon (Si),
Q 3 is a C1 to C30 hydrocarbyl group, or a C1 to C30 hydrocarbyloxy group, and
Q 4 is a C2 to C30 hydrocarbyloxyhydrocarbyl group.
11. The hybrid supported metallocene catalyst of claim 1 ,
wherein the second metallocene compound is represented by one of the following Chemical Formulae 2-1 to 2-4:
in Chemical Formulae 2-1 to 2-4, M 2 , X 3 , X 4 , R a , T 1 , Q 3 , Q 4 , and R 11 to R 16 are the same as defined in claim 1 .
12. The hybrid supported metallocene catalyst of claim 1 ,
wherein each of R 11 to R 14 is independently hydrogen or a C1 to C10 hydrocarbyl group; and
each of R 15 and R 16 is independently a C1 to C10 hydrocarbyl group.
13. The hybrid supported metallocene catalyst of claim 1 ,
wherein M 2 is titanium, zirconium, or hafnium, and
each of X 3 and X 4 is independently halogen, or a C1 to C10 alkyl group.
14. The hybrid supported metallocene catalyst of claim 1 ,
wherein the second metallocene compound is represented by one of the following structural formulae:
15. The hybrid supported metallocene catalyst of claim 1 ,
wherein the first metallocene compound and the second metallocene compound are supported in a molar ratio of 1:2 to 5:1.
16. The hybrid supported metallocene catalyst of claim 1 ,
wherein the first metallocene compound is represented by the following Chemical Formula 1-1, and the second metallocene compound is represented by one of the following Chemical Formulae 2-1 to 2-4:
in Chemical Formula 1-1, M 1 , X 1 , X 2 , R 2 , R 7 to R 10 , Q 1 , and Q 2 are the same as defined in claim 1 ,
in Chemical Formulae 2-1 to 2-4, M 2 , X 3 , X 4 , R a , T 1 , Q 3 , Q 4 , and R 11 to R 16 are the same as defined in claim 1 .
17. A process for preparing a polyethylene copolymer, comprising the step of copolymerizing ethylene and alpha-olefin in the presence of the hybrid supported metallocene catalyst of claim 1 .
18. The process for preparing a polyethylene copolymer of claim 17 ,
wherein the alpha-olefin is at least one selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.