IP Library › Granted Patent US 9,610,549

Granted Patent B2

US 9,610,549 · App. 14/827,599 · Granted Apr 4, 2017

Polycyclo-olefinic block copolymers

Inventors: Andrew Bell (Brecksville, OH); Tamami Takigawa (Tokyo, JP)

Assignees: PROMERUS, LLC; SUMITOMO BAKELITE CO., LTD.

B01D71/80 B01D61/362 B01D67/0002 B01D67/0009 B01D67/0095 B01D69/08 B01D69/087 B01D69/12 B01D69/125 C07F15/006 C08F32/04 C08F299/02 B01D2323/12 B01D2323/36 C08F4/80

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Quick Facts

Patent No.: US 9,610,549
App. No.: 14/827,599
Granted: Apr 4, 2017
Kind: B2

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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.

Claims (111)

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-NBANB); and

a block polymer of derived from 5-hexylbicyclo[2.2.1]hept-2-ene and 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (HexNB-b-NBANB).

17. A process for the preparation of a block polymer of 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 respectively first and second monomeric repeat units different from each other and independently derived from a respective first and second monomer of formula (IV):

wherein:

denotes a place of bonding with another repeat unit;

p is an integer 0, 1 or 2;

comprising reacting said first monomer with a palladium compound to form the first polymer block; and reacting said second monomer which is distinct from the first monomer to form the block polymer.

18. The process of claim 17 , which further comprises reacting a third monomer to form a block polymer of formula (VII):

(A) m - b -(B) n - b -(C) o (VII);

where m, n and b are as defined in claim 17 and o is an integer of at least 15; and

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 17 .

19. The process of claim 18 , wherein the polymer formed 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

20. The process of claim 17 , wherein the block polymer formed 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-NBANB); and

a block polymer of derived from 5-hexylbicyclo[2.2.1]hept-2-ene and 2-(bicyclo[2.2.1]hept-5-en-2-yl)bicyclo[2.2.1]heptane (HexNB-b-NBANB).

Assignments (3)

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 18, 2021

From: PROMERUS, LLC

To: SUMITOMO BAKELITE CO., LTD.

Reel/Frame 058154/0563 →

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 21, 2016

From: TAKIGAWA, TAMAMI

To: SUMITOMO BAKELITE CO., LTD.

Reel/Frame 039421/0148 →

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 14, 2016

From: BELL, ANDREW

To: PROMERUS, LLC

Reel/Frame 039159/0547 →

Continuity (5)

Provisional Application 62037809 · Aug 15, 2014

Provisional Application 62037823 · Aug 15, 2014

Provisional Application 62037828 · Aug 15, 2014

Provisional Application 62073013 · Oct 31, 2014

Related Publication 20160046752A1 · Feb 18, 2016