Polycyclo-olefinic block copolymers

Patent metadata

Field	Value
Publication number	US-9610549-B2
Application number	US-201514827599-A
Country	US
Kind code	B2
Filing date	Aug 17, 2015
Priority date	Aug 15, 2014
Publication date	Apr 4, 2017
Grant date	Apr 4, 2017

Abstract

A series of vinyl addition block polymers derived from functionalized norbornene monomers are disclosed and claimed. Specifically, a series of diblock and triblock polymers derived from norbornene monomers are disclosed. Also disclosed are the method of preparation of such block polymers, and their use in the fabrication of membranes which exhibit unique separation properties.

First claim

What is claimed is:

1. A block polymer of the formula (VI):
(A) m - b -(B) n   (VI);

where m and n are integers of at least 15;
b denotes a bond;
A and B are different from each other and independently selected from a repeat unit represented by formula (IVA), said repeat unit is derived from a monomer of formula (IV):

wherein:
denotes a place of bonding with another repeat unit;
p is an integer 0, 1 or 2;
R 3 , R 4 , R 5 and R 6 are the same or different and each independently of one another is selected from hydrogen, linear or branched (C 1 -C 16 )alkyl, hydroxy(C 1 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 3 -C 6 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 2 -C 6 )alkoxy(C 1 -C 2 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy or (C 1 -C 6 )acyloxy, where each of the aforementioned substituents are optionally substituted with a group selected from halogen or hydroxy.

2. The block polymer of claim 1 wherein said block polymer further comprises a third repeat unit and represented by formula (VII):
(A) m - b -(B) n - b -(C) o   (VII);

where m, n and b are as defined in claim 1 and o is an integer of at least 15;
C is same or different from A or B and independently selected from a repeat unit represented by formula (IVA), said repeat unit is derived from a monomer of formula (IV) as defined in claim 1 .

3. The block polymer of claim 2 , wherein the block molar ratio of A:B:C is from 1:1:1 to 1:4:1 to 1:1:4.

4. The block polymer of claim 2 , wherein the block molar ratio of A:B:C is 1:1:1.

5. The block polymer of claim 2 , wherein the block molar ratio of A:B:C is 1:2:1.

6. The block polymer of claim 2 , wherein C is derived from a monomer selected from the group consisting of:
5-butylbicyclo[2.2.1]hept-2-ene (BuNB);
5-hexylbicyclo[2.2.1]hept-2-ene (HexNB);
5-octylbicyclo[2.2.1]hept-2-ene (OctNB);
5-perfluoroethylbicyclo[2.2.1]hept-2-ene (C 2 F 5 NB);
5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (C 4 F 9 NB);
5-perfluorohexylbicyclo[2.2.1]hept-2-ene (C 6 F 13 NB);
norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
1-(3-(bicyclo[2.2.1]hept-5-en-2-yl)propyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (PrDMMINB);
1-(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB);
1-(6-(bicyclo[2.2.1]hept-5-en-2-yl)hexyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (HexDMMINB);
5-phenethylbicyclo[2.2.1]hept-2-ene (PENB); and
2-(bicyclo [2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (NBANB).

7. The block polymer of claim 2 , wherein C is derived from a monomer selected from the group consisting of:
5-butylbicyclo[2.2.1]hept-2-ene (BuNB);
5-hexylbicyclo[2.2.2.1]hept-2-ene (HexNB);
5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (C 4 F 9 NB);
norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
1-(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB); and
2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo [2.2.1]heptane (NBANB).

8. The block polymer of claim 2 , which is selected from the group consisting of:
a block polymer derived from 5-butylbicyclo[2.2.1]hept-2-ene, norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 5-butylbicyclo[2.2.1]hept-2-ene (BuNB-b-HFANB-b-BuNB); and
a block polymer derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol, 5-butylbicyclo[2.2.1]hept-2-ene, and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB-b-BuNB-b-HFANB).

9. The block polymer of claim 1 , wherein the block molar ratio of A:B is from 1:1 to 1:4.

10. The block polymer of claim 1 , wherein the block molar ratio of A:B is from 1:1 to 1:2.

11. The block polymer of claim 1 , wherein the block molar ratio of A:B is 1:1.

12. The block polymer of claim 1 , wherein A is derived from a monomer selected from the group consisting of:
5-butylbicyclo[2.2.1]hept-2-ene (BuNB);
5-hexylbicyclo[2.2.1]hept-2-ene (HexNB);
5-octylbicyclo[2.2.1]hept-2-ene (OctNB);
5-perfluoroethylbicyclo[2.2.1]hept-2-ene (C 2 F 5 NB);
5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (C 4 F 9 NB);
5-perfluorohexylbicyclo[2.2.1]hept-2-ene (C 6 F 13 NB);
norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
1-(3-(bicyclo[2.2.1]hept-5-en-2-yl)propyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (PrDMMINB);
1-(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB);
1-(6-(bicyclo[2.2.1]hept-5-en-2-yl)hexyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (HexDMMINB);
5-phenethylbicyclo[2.2.1]hept-2-ene (PENB); and
2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (NBANB).

13. The block polymer of claim 1 , wherein B is derived from a monomer selected from the group consisting of:
5-butylbicyclo[2.2.1]hept-2-ene (BuNB);
5-hexylbicyclo[2.2.1]hept-2-ene (HexNB);
5-octylbicyclo[2.2.1]hept-2-ene (OctNB);
5-perfluoroethylbicyclo[2.2.1]hept-2-ene (C 2 F 5 NB);
5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (C 4 F 9 NB);
5-perfluorohexylbicyclo[2.2.1]hept-2-ene (C 6 F 13 NB);
norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
1-(3-(bicyclo[2.2.1]hept-5-en-2-yl)propyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (PrDMMINB);
1-(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB);
1-(6-(bicyclo[2.2.1]hept-5-en-2-yl)hexyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (HexDMMINB);
5-phenethylbicyclo[2.2.1]hept-2-ene (PENB); and
2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (NBANB).

14. The block polymer of claim 1 , wherein A is derived from a monomer selected from the group consisting of:
5-butylbicyclo[2.2.1]hept-2-ene (BuNB);
5-hexylbicyclo[2.2.1]hept-2-ene (HexNB);
5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (C 4 F 9 NB);
norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
1-(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB); and
2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (NBANB).

15. The block polymer of claim 1 , wherein B is derived from a monomer selected from the group consisting of:
5-butylbicyclo[2.2.1]hept-2-ene (BuNB);
5-hexylbicyclo[2.2.1]hept-2-ene (HexNB);
5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (C 4 F 9 NB);
norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
1-(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB); and
2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (NBANB).

16. The block polymer of claim 1 , which is selected from the group consisting of:
a block polymer derived from 5-hexylbicyclo[2.2.1]hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HexNB-b-HFANB);
a block polymer derived from 5-butylbicyclo[2.2.1]hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (BuNB-b-HFANB);
a block polymer derived from 5-butylbicyclo[2.2.1]hept-2-ene and 1-(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (C 4 F 9 NB-b-BuDMMINB);
a block polymer of derived from norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (HFANB-b-NBAN

Assignees

• Promerus Llc
• Sumitomo Bakelite Co
• Sumitomo Bakelite Co

Inventors

• Bell Andrew
• Takigawa Tamami

Classifications

• B01D69/125

  In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction · CPC title

• B01D2323/36

  Introduction of specific chemical groups · CPC title

• B01D67/0095

  Drying · CPC title

• B01D61/362

  Pervaporation · CPC title

• B01D69/12

  Composite membranes; Ultra-thin membranes · CPC title