Method for preparing a composition comprising perfluoropolyether having a hydroxyl group at one terminal

Patent metadata

Field	Value
Publication number	US-9951222-B2
Application number	US-201514682290-A
Country	US
Kind code	B2
Filing date	Apr 9, 2015
Priority date	Apr 10, 2014
Publication date	Apr 24, 2018
Grant date	Apr 24, 2018

Abstract

An object of the present invention is to provide a method for efficiently and highly selectively preparing a composition comprising perfluoropolyether having a hydroxyl group at one terminal at a higher ratio. The present invention provides a method for increasing a ratio of perfluoropolyether having a hydroxyl group at one terminal, relative to a total amount of the perfluoropolyether having a hydroxyl group at one terminal and perfluoropolyether having hydroxyl groups at both terminals in a composition comprising these perfluoropolyethers, wherein the method comprises a step of subjecting the composition to chromatography in which a moving phase is supercritical or subcritical state carbon dioxide of the specific temperature and the specific pressure, and a stationary phase is silica gel to thereby collect a fraction containing the perfluoropolyether having a hydroxyl group at one terminal at a higher ratio. Further, present invention provides for increasing a ratio of perfluoropolyether having a hydroxyl group at one terminal, relative to a total amount of the perfluoropolyether having a hydroxyl group at one terminal, perfluoropolyether having hydroxyl groups at both terminals and perfluoropolyether having no hydroxyl group at any terminal perfluoropolyether, in a composition comprising these perfluoropolyethers, wherein the method comprises a step of subjecting the composition to chromatography in which a moving phase is supercritical or subcritical state carbon dioxide of the specific temperature and the specific pressure, and a stationary phase is silica gel to thereby collect a fraction containing the perfluoropolyether having a hydroxyl group at one terminal at a higher ratio.

First claim

The invention claimed is:

1. A method for increasing a ratio of perfluoropolyether having a hydroxyl group at one terminal to 80 mole % or more, relative to a total amount of the perfluoropolyether having a hydroxyl group at one terminal, perfluoropolyether having hydroxyl group at both terminals and perfluoropolyether having no hydroxyl group at any terminal where the perfluoropolyether having no hydroxyl group at any terminal is hereinafter referred to as non-functionalized perfluoropolyether,
said perfluoropolyether having a hydroxyl group at one terminal is represented by the following formula (a):
A-Rf—B  (a)

wherein Rf is a linear or branched polyfluorooxyalkylene group having 10 to 500 repeating units which are, independently of each other, represented by the formula: —OC j F 2j —, wherein j is an integer of from 1 to 6, and A and B are a hydroxyl group or a —CF 3 group and either of A and B is a hydroxyl group,

the method comprising the steps of subjecting a composition feed stock comprising perfluoropolyether having one terminal hydroxyl group, perfluoropolyether having both terminal end hydroxyl groups and non-functionalized perfluoropolyether to chromatography in which a moving phase is a supercritical or subcritical state carbon dioxide and a stationary phase is silica gel and the chromatography comprises the following step (i′) or (ii′):
(i′) the moving phase is at a constant temperature, T 0 , of 25 degrees C. or higher to 150 degrees C. or lower and a constant pressure, P 1 , of 7 MPa or higher to lower than 30 MPa to thereby collect a fraction containing the non-functionalized perfluoropolyether at a higher ratio and, subsequently, the pressure of the moving phase is increased to a constant pressure, P 2 , which is higher than 7 MPa to 30 MPa or lower and is higher than the aforesaid pressure P 1
and a step of collecting a fraction containing the perfluoropolyether having a hydroxyl group at one terminal at 80 mole % or more;
(ii′) the moving phase is at a constant temperature, T 1 , of higher than 25 degrees C. to 150 degrees C. or lower and a constant pressure, P 0 , of 7 MPa or higher to 30 MPa or lower to thereby collect a fraction containing the non-functionalized perfluoropolyether at a higher ratio and, subsequently, the temperature of the moving phase is decreased to a constant temperature, T 2 , which is 25 degrees C. or higher to lower than 150 degrees C. and is lower than the aforesaid temperature T 1
and a step of collecting a fraction containing the perfluoropolyether having a hydroxyl group at one terminal at 80 mole % or more.

2. The method according to claim 1 , wherein the aforesaid chromatography further comprises the following step (i″) after aforesaid step (i′) or the following step (ii″) after aforesaid step (ii′),
(i″) the pressure of the moving phase is increased to a constant pressure, P 3 , which is higher than 7 MPa to 35 MPa or lower and is higher than the aforesaid pressure P 2 to thereby collect a fraction containing the perfluoropolyether having hydroxyl groups at both terminals at a higher ratio;
(ii″) the temperature of the moving phase is decreased to a constant temperature, T 3 , which is 25 degrees C. or higher to lower than 100 degrees C. and is lower than the aforesaid temperature, T 2 , to thereby collect a fraction containing the perfluoropolyether having hydroxyl groups at both terminals at a higher ratio.

3. The method according to claim 1 or 2 , wherein the silica gel in such that a water dispersion containing 10 weight % of the silica gel has pH between 5 and 10 at 25 degrees C.

4. The method according to claim 1 , wherein the fraction containing the perfluoropolyether having a hydroxyl group at one terminal contains perfluoropolyether having a hydroxyl group at one terminal in an amount of 86 mole % or more, relative to a total mole of perfluoropolyethers in the fraction containing the perfluoropolyether having a hydroxyl group at one terminal.

5. The method according to claim 3 , wherein the composition before subjected to said chromatography is one prepared by the following steps:
1) a step of fluorinating a part of non-hydroxyl functional groups of perfluoropolyether having the functional groups at the both terminals; and
2) a step of converting the remaining functional group into a hydroxyl group.

6. The method according to claim 5 , wherein the functional group is a carboxyl group or an acid fluoride group.

7. The method according to claim 4 , wherein the Rf is a polyfluorooxyalkylene group represented by the following formula:
—(CF 2 ) d —(OCF 2 ) p (OCF 2 CF 2 ) q (OCF 2 CF 2 CF 2 ) r (OCF 2 CF 2 CF 2 CF 2 ) s —O(CF 2 ) d —

wherein d is an integer of from 0 to 5, p and q are, independently of each other, an integer of from 5 to 300, r and s are, independently of each other, an integer of from 0 to 100, and a total of p, q, r and s is 10 to 500, and the parenthesized units may be sequenced at random.

8. The method according to claim 1 , wherein the Rf is a linear polyfluorooxyalkylene group represented by the following formula:
—(CF 2 ) d —(OCF 2 ) p (OCF 2 CF 2 ) q (OCF 2 CF 2 CF 2 ) r (OCF 2 CF 2 CF 2 CF 2 ) s —O(CF 2 ) d —

wherein d is an integer of from 0 to 5, p and q are, independently of each other, an integer of from 5 to 300, r and s are, independently of each other, an integer of from 0 to 100, and a total of p, q, r and s is 10 to 500, and the parenthesized units may be sequenced at random.

Assignees

• Shinetsu Chemical Co

Inventors

• Yamane Yuji
• Matsuda Takashi
• Koike Noriyuki

Classifications

• C08G65/007 Primary

  containing fluorine · CPC title

• Y02P20/544

  Cross-Sectional Technologies · mapped topic

• C08G65/46

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

• C08G65/30

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

• B01D15/12

  relating to the preparation of the feed · CPC title