Thermosensitive copolymers, forward osmosis water treatment devices including the same, and methods of producing and using the same

Patent metadata

Field	Value
Publication number	US-9447239-B2
Application number	US-201313845471-A
Country	US
Kind code	B2
Filing date	Mar 18, 2013
Priority date	Mar 19, 2012
Publication date	Sep 20, 2016
Grant date	Sep 20, 2016

Abstract

A thermosensitive copolymer may include a first repeating unit having a temperature-sensitive oligomer and a second repeating unit having an ionic moiety and a counter ion to the ionic moiety. The temperature-sensitive oligomer may be an oligomer including a repeating unit derived from a unsaturated monomer with a moiety represented by Chemical Formula 1 or Chemical Formula 2, or an oligomer including a repeating unit derived from a heterocyclic compound having C, N, O, and a C═N bond in its ring.

*—C(═O)N(R 2 )(R 3 )  [Chemical Formula 1]

R 2 and R 3 may each independently be hydrogen or a linear or branched C1 to C6 alkyl group, a C3 to C7 cycloalkyl group, or a C6 to C10 aryl group, R 2 and R 3 may not both be hydrogen, and R 2 and R 3 may be combined to form a nitrogen containing heterocycle.

R 4 may be a C2 to C5 alkylene group.

First claim

What is claimed is:

1. A thermosensitive copolymer, comprising:
a first repeating unit and a second repeating unit, the first repeating unit having a temperature-sensitive oligomer, the second repeating unit having an ionic moiety and a counter ion bonded to the ionic moiety, the temperature sensitive oligomer being grafted onto the first repeating unit, and the first repeating unit and the second repeating unit being linked to form a polyamino acid backbone;
wherein the first repeating unit is represented by Chemical Formula 6-1, and the second repeating unit is represented by Chemical Formula 6-2,

A − being a group including the ionic moiety, M + being the counter ion, Q being —NR 5 — or —S—, R 5 being hydrogen or a C1 to C5 alkyl group, L being a direct bond, a substituted or unsubstituted C1 to C20 alkylene, or a substituted or unsubstituted C1 to C20 thioalkylene, Og being a temperature sensitive oligomer selected from the group consisting of a first temperature sensitive oligomer including a repeating unit of Chemical Formula 7, a second temperature sensitive oligomer including a repeating unit of Chemical Formula 8, and a third temperature sensitive oligomer including a repeating unit of Chemical Formula 9,

R 1 being hydrogen or methyl, wherein R 2 and R 3 are:
(a) each independently, but not simultaneously, being hydrogen,
(b) a chemical group, the chemical group is selected from the group consisting of at least one of a linear or branched C1 to C6 alkyl group, C3 to C7 cycloalkyl group, and a C6 to C10 aryl group, or
(c) combinable to form a nitrogen containing heterocycle,

R 4 being a C2 to C5 alkylene group,

Ak being a linear or branched C1 to C10 alkyl group, R independently being hydrogen or a C1 to C3 alkyl group,
wherein,
the temperature-sensitive oligomer has a polymerization degree of about 2 to about 30,
the ionic moiety of the second repeating unit is an anionic moiety selected from the group consisting of —COO—, —SO 3 − , —PO 3 2− ,

a mole ratio of the first repeating unit to the second repeating unit is about 1:99 to about 40:60, and the thermosensitive copolymer has a lower critical solution temperature (LCST) of about 10° C. to about 50° C. at a concentration of 0.01 g/ml, and
the copolymer is structured to dissolve in water at a temperature lower than 10° C.

2. The thermosensitive copolymer of claim 1 , wherein the third temperature sensitive oligomer is a polymerization product of a heterocyclic compound and the heterocyclic compound is selected from the group consisting of 2-methyl-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-isopropyl-2-oxazoline, 2-butyl-2-oxazoline, 2-isobutyl-2-oxazoline, 2-pentyl-2-oxazoline, and 2-isopentyl-2-oxazoline.

3. The thermosensitive copolymer of claim 1 , wherein,
the first temperature sensitive oligomer is a polymerization product of an N-alkyl(meth)acryl amide and the N-alkyl(meth)acryl amide is selected from the group consisting of N-isopropyl(meth)acrylamide (NIPAAm), N-isobutyl(meth)acrylamide, N-isopentyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-ethylmethyl(meth)acrylamide, and N,N-diethyl(meth)acrylamide (DEAAM), and
the second temperature sensitive oligomer is a polymerization product of an N-vinyl lactam and the N-vinyl lactam is selected from the group consisting of N-vinyl caprolactam (VCL), N-vinyl-2-pyrrolidone, and N-vinyl-piperidone.

4. The thermosensitive copolymer of claim 1 , wherein the first temperature-sensitive oligomer further includes a repeating unit derived from (meth)acrylamide.

5. The thermosensitive copolymer of claim 1 , wherein the temperature-sensitive oligomer has a polymerization degree of about 4 to about 25.

6. The thermosensitive copolymer of claim 1 , wherein the thermosensitive copolymer has a number average molecular weight of about 5,000 to about 100,000.

7. The thermosensitive copolymer of claim 1 , wherein the thermosensitive copolymer includes at least two second repeating units and each of the at least two second repeating units includes a different ionic moiety.

8. The thermosensitive copolymer of claim 1 , wherein the counter ion is selected from the group consisting of an alkali metal cation and an alkaline earth metal cation.

9. The thermosensitive copolymer of claim 1 , wherein the mole ratio of the first repeating unit to the second repeating unit is about 1:99 to about 10:90.

10. The thermosensitive copolymer of claim 1 , wherein
A − is selected from the group consisting of —COO—, —CONR—Z—, —CONR—Z—O—PO 3 2− , —CO—S—Z—SO 3 − , and —CO—S—Z—O-PO 3 2− , Z is a substituted or unsubstituted C1 to C20 alkylene group, and M + is selected from the group consisting of Na + , K + , Li + , Ca 2+ , Mg 2+ , and Ba 2+ .

11. The thermosensitive copolymer of claim 1 , wherein the thermosensitive copolymer has a number average molecular weight of about 5,000 to about 250,000.

12. The thermosensitive copolymer of claim 1 , wherein the copolymer forms an aggregated particle and the aggregated particle is precipitated at a temperature of higher than or equal to the LCST.

13. A method of producing the thermosensitive copolymer of claim 1 , comprising:
preparing a polysuccinimide;
preparing the temperature-sensitive oligomer having an amine group or a thiol group at one end and including a repeating unit derived from a monomer represented by Chemical Formula 3, Chemical Formula 4, Chemical Formula 5, or a combination thereof,

Ak being a linear or branched C1 to C10 alkyl group, R independently being hydrogen or a C1 to C3 alkyl group,

R 1 being hydrogen or methyl, R 2 and R 3 each independently being hydrogen, a linear or branched C1 to C6 alkyl group, a C3 to C7 cycloalkyl group, or a C6 to C10 aryl group, R 2 and R 3 not simultaneously being hydrogen, R 2 and R 3 being combinable to form a nitrogen containing heterocycle,

R 4 being a C2 to C5 alkylene group;
subjecting the polysuccinimide to a first reaction with the temperature-sensitive oligomer so as to open one or more succinimide rings in the polysuccinimide and to graft the temperature-sensitive oligomer thereto to form a reaction product; and
subjecting the reaction product to a second reaction with an amine compound having an ionic moiety, a thiol compound having the ionic moiety, an inorganic base, or a combination thereof to open a remainder of the succinimide rings in the polysuccinimide and to introduce the ionic moiety and a counter ion to produce the thermosensitive copolymer, the thermosensitive copolymer including a first repeating unit and a second repeating unit, the first repeating unit having the temperature-sensitive oligomer, the second repeating unit having the ionic moiety and the counter ion bonded to the ionic moiety.

14. The method of producing a thermosensitive copolymer

Assignees

• Samsung Electronics Co Ltd

Inventors

• Jung Bo Kyung
• Kim Jae Eun
• Han Sung Soo
• Kang Hyo
• Kang Hyo Rang
• Han Jung Im

Classifications

• C08G69/42 Primary

  Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen (C08G69/12, C08G69/32 take precedence) · CPC title

• C08G73/10

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title

• C02F1/445 Primary

  by forward osmosis · CPC title

• B01D61/002

  Forward osmosis or direct osmosis · CPC title

• Y02P20/10

  Process efficiency · CPC title