Method for separating perfluoro(poly)ether-group-containing alcohol compounds

Patent metadata

Field	Value
Publication number	US-11155678-B2
Application number	US-201716327611-A
Country	US
Kind code	B2
Filing date	Aug 24, 2017
Priority date	Aug 25, 2016
Publication date	Oct 26, 2021
Grant date	Oct 26, 2021

Abstract

A method for chromatographically separating a mixture containing a perfluoro(poly)ether group-containing monoalcohol compound represented by the following formula (2) and a perfluoro(poly)ether group-containing dialcohol compound represented by the following formula (3):A-Pf-Z  (2)Z-Pf-Z  (3)wherein Pf represents a divalent perfluoropolyether group and A and Z are as defined herein, the method including: adsorbing the mixture onto a stationary phase, and eluting the perfluoro(poly)ether group-containing monoalcohol compound represented by formula (2) by one mobile phase selected from hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoroethers, fluorine-containing ester solvents, and fluorine-containing aromatic solvents to separate the perfluoro(poly)ether group-containing monoalcohol compound represented by formula (2) from the perfluoro(poly)ether group-containing dialcohol compound represented by formula (3).

First claim

The invention claimed is:

1. A method for chromatographically separating a mixture comprising a perfluoro(poly)ether group-containing monoalcohol compound represented by the following formula (2) and a perfluoro(poly)ether group-containing dialcohol compound represented by the following formula (3):
A-Pf-Z  (2)

Z-Pf-Z  (3)

wherein
Pf represents a divalent perfluoropolyether group,
A each independently represents an R 1 — group, an R 1 —O— group, an R 2 O—CH 2 —R 3 — group, or an R 2 O—CH 2 —R 3 —O— group,
R 1 each independently represents an alkyl group,
R 2 each independently represents an alkyl group,
R 3 each independently represents a divalent organic group containing 1 to 4 carbon atoms,
Z each independently represents an —R 5 —CH 2 OH group or an —O—R 5 —CH 2 OH group, and
R 5 each independently represents a bond or a divalent organic group containing 1 to 4 carbon atoms,
the method comprising:
adsorbing the mixture onto a stationary phase by using the same solvent as a solvent used as a mobile phase described below, and
eluting the perfluoro(poly)ether group-containing monoalcohol compound represented by formula (2) by one mobile phase of a single solvent in a liquid state selected from the group consisting of hydrochlorofluorocarbons, hydrofluoroethers, fluorine-containing ester solvents, and fluorine-containing aromatic solvents to separate the perfluoro(poly)ether group-containing monoalcohol compound represented by formula (2) from the perfluoro(poly)ether group-containing dialcohol compound represented by formula (3).

2. The method according to claim 1 , further comprising increasing a temperature of the stationary phase to elute the perfluoro(poly)ether group-containing dialcohol compound represented by formula (3) by one mobile phase of a single solvent in a liquid state selected from the group consisting of hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoroethers, fluorine-containing ester solvents, and fluorine-containing aromatic solvents after separating the perfluoro(poly)ether group-containing monoalcohol compound represented by formula (2).

3. A method for chromatographically separating a mixture comprising:
a perfluoro(poly)ether group-containing nonalcohol compound represented by the following formula (1),
a perfluoro(poly)ether group-containing monoalcohol compound represented by the following formula (2), and
a perfluoro(poly)ether group-containing dialcohol compound represented by the following formula (3):
A-Pf-A  (1)

A-Pf-Z  (2)

Z-Pf-Z  (3)

wherein
Pf represents a divalent perfluoropolyether group,
A each independently represents an R 1 — group, an R 1 —O— group, an R 2 O—CH 2 —R 3 — group, or an R 2 O—CH 2 —R 3 —O— group,
R 1 each independently represents an alkyl group,
R 2 each independently represents an alkyl group,
R 3 each independently represents a divalent organic group containing 1 to 4 carbon atoms,
Z each independently represents an —R 5 —CH 2 OH group or an —O—R 5 —CH 2 OH group, and
R 5 each independently represents a bond or a divalent organic group containing 1 to 4 carbon atoms,
the method comprising:
(i) adsorbing the mixture onto a stationary phase,
(ii) eluting the perfluoro(poly)ether group-containing nonalcohol compound represented by formula (1) by a mobile phase selected from nonpolar solvents and low-polarity solvents to separate the perfluoro(poly)ether group-containing nonalcohol compound represented by formula (1) from the perfluoro(poly)ether group-containing monoalcohol compound represented by formula (2) and the perfluoro(poly)ether group-containing dialcohol compound represented by formula (3),
(iii) eluting the perfluoro(poly)ether group-containing monoalcohol compound represented by formula (2) by one mobile phase of a single solvent in a liquid state selected from the group consisting of hydrochlorofluorocarbons, hydrofluoroethers, fluorine-containing ester solvents, and fluorine-containing aromatic solvents to separate the perfluoro(poly)ether group-containing monoalcohol compound represented by formula (2) from the perfluoro(poly)ether group-containing dialcohol compound represented by formula (3), and
(iv) increasing a temperature of the stationary phase to elute the perfluoro(poly)ether group-containing dialcohol compound represented by formula (3) by one mobile phase of a single solvent in a liquid state selected from the group consisting of hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoroethers, fluorine-containing ester solvents, and fluorine-containing aromatic solvents.

4. The method according to claim 2 , wherein a column temperature when eluting the perfluoro(poly)ether group-containing dialcohol compound represented by formula (3) is 50 to 150° C.

5. The method according to claim 1 , wherein Pf is a perfluoro(poly)ether group represented by:

wherein a, b, c, and d are each independently an integer of 0 or 1 or more; the sum of a, b, c, and d is at least 1; and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula.

6. The method according to claim 3 , wherein in formula (1) or (2), R 1 is each independently a C 1-16 perfluoroalkyl group, HCF 2 (CF 2 ) g —, or ClCF 2 (CF 2 ) g —, and g is an integer of 0 or more and 15 or less.

7. The method according to claim 5 , wherein b is an integer of 1 or more and 200 or less, and a, c, and d are 0.

8. The method according to claim 5 , wherein a and b are each independently an integer of 0 or more and 30 or less, and c and d are each independently an integer of 1 or more and 200 or less.

9. The method according to claim 3 , wherein Pf in formulae (1) to (3) has a number average molecular weight of 500 to 100,000.

10. The method according to claim 1 , wherein the mobile phase for eluting the perfluoro(poly)ether group-containing monoalcohol compound represented by formula (2) is m-xylene hexafluoride, perfluorobenzene, perfluorohexyl methyl ether, perfluorobutyl ethyl ether, perfluorobutyl methyl ether, HCFC-225, or ethyl trifluoroacetate.

11. A method for producing a perfluoro(poly)ether group-containing monoalcohol compound represented by the following formula (2):
A-Pf-Z  (2)

wherein
Pf represents a divalent perfluoropolyether group,
A each independently represents an R 1 — group, an R 1 —O— group, an R 2 O—CH 2 —R 3 — group, or an R 2 O—CH 2 —R 3 —O— group,
R 1 each independently represents an alkyl group,
R 2 each independently represents an alkyl group,
R 3 each independently represents a divalent organic group containing 1 to 4 carbon atoms,
Z each independently represents an —R 5 —CH 2 OH group or an —O—R 5 —CH 2 OH group, and
R 5 each independently represents a bond or a divalent organic group containing 1 to 4 carbon atoms,

the method comprising:
adsorbing a mixture comprising the perfluoro(poly)ether group-containing monoalcohol compound represented by formula (2) and a perfluoro(poly)ether group-containing dialcohol compound represented by the following formula (3):
Z-Pf-Z  (3)

wherein Pf, A, and Z are as defined above onto a stationary phase by using the same solvent as a solvent used as a mobile phase described below, and eluting the perfluoro(poly)ether group-containing monoalcohol compound represented by formula (2) from the mixture, by using one mobile phase of a single solvent in a liquid state selected from the group consisting of hydrochlorofluorocarbons, hydrofluoroethers, fluorine-containing ester solvents, and fluorine-containing aromatic solvents in chromatography

Assignees

• Daikin Ind Ltd

Inventors

• Naitou Masato
• Nomura Takashi
• Takano Shinya

Classifications

• B01D15/426 Primary

  Specific type of solvent · CPC title

• B01D15/3876

  modifying the temperature · CPC title

• C08G65/30 Primary

  Post-polymerisation treatment, e.g. recovery, purification, drying · CPC title

• B01D15/34

  Size-selective separation, e.g. size-exclusion chromatography; Gel filtration; Permeation · CPC title