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

Patent metadata

Field	Value
Publication number	US-10533069-B2
Application number	US-201615749157-A
Country	US
Kind code	B2
Filing date	Jul 29, 2016
Priority date	Jul 31, 2015
Publication date	Jan 14, 2020
Grant date	Jan 14, 2020

Abstract

The present disclosure relates to a cyclic polysulfane-based polymer, a cyclic polysulfane-polynorbornene block copolymer, a method of preparing the cyclic polysulfane-based polymer, a method of preparing the cyclic polysulfane-polynorbornene block copolymer, and a film including the cyclic polysulfane-polynorbornene block copolymer.

First claim

We claim:

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-

Assignees

• Seoul Nat Univ R&Db Foundation
• Seoul National Univ Rdb Foudation

Inventors

• Char Kookheon
• Lim Jeewoo
• Choi Tae-Lim
• Cho Yunshik
• Kang Eun-Hye
• Yang Sanghee

Classifications

• C08G61/12

  Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule · CPC title

• C08G61/08 Primary

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title

• C08G2261/418

  Ring opening metathesis polymerisation [ROMP] · CPC title

• C08F4/7006

  NN · CPC title

• C08G2261/126

  block · CPC title