Cyclic polysulfane-based polymer, method for preparing same, and film comprising same

1. A cyclic polysulfane-based polymer,

which is obtained by polymerization of a sulfur-containing cyclic olefin monomer represented by any one of the following Chemical Formulas 1-1 to 1-3:

wherein,

in Chemical Formulas 1-1 to 1-3,

x may be from 1 to 5;

each of R 1 , R 2 , R 5 and R 6 may be independently H, an alkyl group, a halogen, —OR wherein R is a C1 to C25 linear or branched alkyl group or an isomer thereof, or —COOR′ wherein R′ is a C1 to C25 linear or branched alkyl group or an isomer thereof;

each of R 3 and R 4 may be independently H or an alkyl group;

Y may be NH, O, or S; and

Z may be O or S.

2. The cyclic polysulfane-based polymer of claim 1 ,

wherein the cyclic polysulfane-based polymer includes one represented by any one of the following Chemical Formulas 2-1 to 2-3:

wherein,

in Chemical Formulas 2-1 to 2-3,

m is from 1 to 1000;

x is 1 to 5;

each of R 1 , R 2 , R 5 , and R 6 may be independently H, an alkyl group, a halogen, —OR wherein R is a C1 to C25 linear or branched alkyl group or an isomer thereof, or —COOR′ wherein R′ is a C1 to C25 linear or branched alkyl group or an isomer thereof;

each of R 3 and R 4 may be independently H or an alkyl group;

Y may be NH, O, or S; and

Z may be O or S.

3. A cyclic polysulfane-polynorbornene block copolymer,

which is obtained by copolymerizing a sulfur-containing cyclic olefin monomer represented by any one of Chemical Formulas 1-1 to 1-3defined in claim 1 with a norbornene-based monomer represented by any one of the following Chemical Formulas 3-1 to 3-6:

wherein,

in Chemical Formulas 3-1 to 3-6,

each of R′ 1 , R′ 2 , R′ 5 , and R′ 6 may independently be H, an alkyl group, a halogen, —OR wherein R is a C1 to C25 linear or branched alkyl group or an isomer thereof, or —COOR′ wherein R′ is a C1 to C25 linear or branched alkyl group or an isomer thereof;

each of R′ 3 and R′ 4 may be independently H or an alkyl group;

R′ 7 may be an alkyl group or a cycloalkyl group;

Y′ may be NH, O, or S;

Z′ may be O or S; and

each of R′ 8 , R′ 9 , R′ 10 , and R′ 11 may be independently H, an alkyl group, a halogen, —OR wherein R is a C1 to C25 linear or branched alkyl group or an isomer thereof or —COOR′ wherein R′ is a C1 to C25 linear or branched alkyl group or an isomer thereof.

4. The cyclic polysulfane-polynorbornene block copolymer according to claim 3 ,

wherein the cyclic polysulfane-polynorbornene block copolymer includes one represented by any one of the following Chemical Formulas 4-1 to 4-18:

wherein,

in Chemical Formulas 4-1 to 4-18,

each of n and m is 1 to 1000;

x is 1 to 5;

each of R 1 , R 2 , R 5 , and R 6 may be independently H, an alkyl group, a halogen, —OR wherein R is a C1 to C25 linear or branched alkyl group or an isomer thereof, or —COOR′ wherein R′ is a C1 to C25 linear or branched alkyl group or an isomer thereof;

each of R 3 and R 4 may be independently H or an alkyl group;

each of R′ 1 , R′ 2 , R′ 5 ,and R′ 6 may be independently H, an alkyl group, a halogen, —OR wherein R is a C1 to C25 linear or branched alkyl group or an isomer thereof, or —COOR′ wherein R′ is a C1 to C25 linear or branched alkyl group or an isomer thereof;

each of R′ 3 and R′ 4 may be independently H or an alkyl group;

R′ 7 may be an alkyl group or a cycloalkyl group,

each of R′ 8 , R′ 9 , R′ 10 , and R′ 11 may be independently H, an alkyl group, a halogen, —OR wherein R is a C1 to C25 linear or branched alkyl group or an isomer thereof, or —COOR′ wherein R′ is a C1 to C25 linear or branched alkyl group or an isomer thereof;

Y and Y′ may be NH, O, or S; and

Z and Z′ may be O or S.

5. The cyclic polysulfane-polynorbornene block copolymer according to claim 3 ,

wherein a ratio of the cyclic polysulfane block to the polynorbornene block in the cyclic polysulfane-polynorbornene block copolymer is in the range of 1:0.001 to 1000.

6. The cyclic polysulfane-polynorbornene block copolymer according to claim 3 ,

wherein the cyclic polysulfane-polynorbornene block copolymer has solubility in an organic solvent.

7. The cyclic polysulfane-polynorbornene block copolymer according to claim 3 ,

wherein the cyclic polysulfane-polynorbornene block copolymer has a nanoparticular form.

8. The cyclic polysulfane-polynorbornene block copolymer according to claim 7 ,

wherein the nanoparticle of the cyclic polysulfane-polynorbornene block copolymer exhibits thermal stability.

9. The cyclic polysulfane-polynorbornene block copolymer according to claim 7 ,

wherein the cyclic polysulfane-polynorbornene block copolymer includes the nanoparticle in a micelle form in which the polynorbornene block forms a shell on a core containing the cyclic polysulfane.

10. The cyclic polysulfane-polynorbornene block copolymer according to claim 3 ,

wherein the cyclic polysulfane-polynorbornene block copolymer has transmittance to visible light or light having a wavelength of from 400 nm to 1200 nm.

11. A film, comprising the cyclic polysulfane-polynorbornene block copolymer according to claim 3 .

12. The film according to claim 11 ,

wherein the film comprising the cyclic polysulfane-polynorbornene block copolymer has an improved refractive index as compared to a polynorbornene polymer.

13. The film according to claim 12 ,

wherein a refractive index of the film comprising the cyclic polysulfane-polynorbornene block copolymer exhibits a refractive index increase of 0.02 or more in a range of visible light and/or near infrared light as compared with a polynorbornene polymer.

14. A method of preparing the cyclic polysulfane-based polymer according to claim 1 , comprising:

one-pot polymerizing a sulfur-containing cyclic olefin monomer represented by any one of Chemical Formulas 1-1 to 1-3 defined in claim 1 in the presence of a phosphine-free third generation Grubbs catalyst to obtain the cyclic polysulfane-based polymer.

15. The method of claim 14 ,

wherein the catalyst is represented by the following Chemical Formula 5-1 or 5-2:

wherein,

in Chemical Formulas 5-1 and 5-2,

X may be halogen;

each of R″ 1 and R″ 2 may be independently H, an alkyl group, a halogen, —OR wherein R is a C1 to C25 linear or branched alkyl group or an isomer thereof, or —COOR′ wherein R′ is a C1 to C25 linear or branched alkyl group or an isomer thereof; and

each of Ar 1 and Ar 2 may be independently phenyl group which may be substituted by a linear or branched alkyl group.

16. A method of preparing the cyclic polysulfane-polynorbornene block copolymer according to claim 3 , comprising:

polymerizing a soluble norbornene-based monomer represented by any one of Chemical Formulas 3-1 to 3-6 defined in claim 3 in the presence of a phosphine-free third-generation Grubbs catalyst; and

followed by copolymerization with a sulfur-containing cyclic olefin monomer represented by any one of the Chemical Formulas 1-1 to 1-3 to form a cyclic polysulfane-polynorbornene block copolymer.

17. The method of claim 16 ,

wherein the catalyst is represented by the following Chemical Formula 5-1 or 5-2:

wherein,

in Chemical Formulas 5-1 and 5-2,

X may be halogen;

each of R″ 1 and R″ 2 may be independently H, an alkyl group, a halogen, —OR wherein R is a C1 to C25 linear or branched alkyl group or an isomer thereof, or —COOR′ wherein R′ is a C1 to C25 linear or branched alkyl group or an isomer thereof; and

each of Ar 1 and Ar 2 may be independently phenyl group which may be substituted by a linear or branched alkyl group.