(Per)fluoropolyether polymers

Patent metadata

Field	Value
Publication number	US-11427680-B2
Application number	US-201716469636-A
Country	US
Kind code	B2
Filing date	Dec 12, 2017
Priority date	Dec 14, 2016
Publication date	Aug 30, 2022
Grant date	Aug 30, 2022

Abstract

The present invention relates to a novel process for the synthesis of (per)fluoropolyether polymers, to certain novel (per)fluoropolyether polymers. The present invention also relates to the use of the (per)fluoropolyether polymers thus obtained as intermediate compounds for the manufacture of further polymers suitable for use as lubricants, notably for magnetic recording media (MRM).

First claim

The invention claimed is:

1. A process (P FH ) for the synthesis of at least one polymer (FH), said polymer (FH) comprising a partially fluorinated polyether backbone having two chain ends, wherein said chain ends comprise at least one group selected from hydroxy group, allyl group and vinyl group, said process (P FH ) comprising:
(I) contacting at least one compound (F), wherein compound (F) is a perfluoro compound comprising at least two unsaturated groups selected from vinyl groups and allyl groups, with at least one compound (H), wherein compound (H) is a fully or partially hydrogenated compound comprising at least two hydroxy groups,
to provide a polymer (FH),
said polymer (FH) being characterized in that its backbone comprises recurring unit(s) derived from said at least one compound (F) alternately arranged with recurring unit(s) derived from said at least one compound (H).

2. The process according to claim 1 , wherein
said compound (F) complies with the following formula:
CF 2 ═CF(CF 2 ) z OR CF O(CF 2 ) z* CF═CF 2

wherein
each of z and z* is independently 0 or 1; and
R CF is a perfluoro alkylene chain comprising from 1 to 20 carbon atoms and
optionally interrupted by one or more oxygen atoms; and/or

said compound (H) complies with the following formula:
HO—(R H )—OH

wherein
R H is a linear or branched alkylene chain comprising from 2 to 12 carbon atoms,
said alkyl chain optionally comprising one or more fluorine atoms(s) and optionally being interrupted by one or more oxygen atoms.

3. The process according to claim 1 , wherein step (I) comprises adding, to said compound (F) and to said compound (H), one or more compound (F-mono), wherein compound (F-mono) is a compound comprising one unsaturated group selected from vinyl group and allyl group, and/or one compound (H-mono), wherein compound (H-mono) is a compound comprising one hydroxy group.

4. A polymer (FH*) comprising a partially fluorinated polyether backbone having two chain ends, wherein
each of said chain ends comprises a group selected from hydroxy group, allyl group or vinyl group; and
said backbone complies with structure (R FH -I):
—[CF 2 CFH(CF 2 ) z OR CF O(CF 2 ) z* CFHCF 2 —OR H O] y —  (R FH -I)

wherein
each of z and z* is independently 0 or 1;
R CF is a perfluoro alkylene chain comprising from 1 to 20 carbon atoms and optionally interrupted by one or more oxygen atoms;
R H is a linear or branched alkylene chain comprising from 2 to 12 carbon atoms, said alkyl chain optionally comprising one or more fluorine atoms and optionally being interrupted by one or more oxygen atoms; and
y is an integer, such that the average number molecular weight of the backbone of said polymer (FH) as determined by NMR analysis is from 306 to 50000.

5. The polymer (FH*) according to claim 4 , wherein said polymer (FH*) is selected from polymers of formulae (FH b1 ) to (FH b3 ):
CF 2 ═CF(CF 2 ) z OR CF O(CF 2 ) z* CFHCF 2 —OR H O—[CF 2 CFH(CF 2 ) z OR CF O(CF 2 ) z* CFHCF 2 —OR H O] y —CF 2 CFH(CF 2 ) z OR CF O(CF 2 ) z* CF═CF 2   (FH b1 )

HO—R H —O[CF 2 CFH(CF 2 ) z O—R CF —O(CF 2 ) z* CFHCF 2 —OR H O] y —H  (FH b2 )

CF 2 ═CF(CF 2 ) z OR CF O(CF 2 ) z* CFHCF 2 —OR H O—[CF 2 CFH(CF 2 ) z OR CF O(CF 2 ) z* CFHCF 2 —OR H O] y —H  (FH b3 )

wherein
each of z and z* is independently 0 or 1;
R CF is a perfluoro alkylene chain comprising from 1 to 20 carbon atoms and optionally interrupted by one or more oxygen atoms;
R H is a linear or branched alkylene chain comprising from 2 to 12 carbon atoms, said alkyl chain optionally comprising one or more fluorine atoms and optionally being interrupted by one or more oxygen atoms; and
y is an integer, such that the average number molecular weight of the backbone of said polymer (FH) as determined by NMR analysis is from 306 to 50000.

6. A process (P PFPE ) for the synthesis of a polymer (PFPE), said polymer (PFPE) comprising a perfluorinated polyether backbone having two chain ends, wherein each chain end comprises at least one group selected from
—OC(═O)F and perfluorinated alkyl chain comprising from 2 to 3 carbon atoms, said process (P PFPE ) comprising:
(III) contacting at least one polymer (FH) or polymer (FH*) with a source of fluorine, to provide polymer (PFPE), wherein:
polymer (FH) is a polymer comprising a partially fluorinated polyether backbone having two chain ends, wherein
each of said chain ends comprise at least one group selected from hydroxy group, allyl group and vinyl group; and
said backbone comprises recurring unit(s) derived from at least one compound (F), wherein compound (F) is a perfluoro compound comprising at least two unsaturated groups selected from vinyl groups and allyl groups, alternately arranged with recurring unit(s) derived from at least one compound (H), wherein compound (H) is a fully or partially hydrogenated compound comprising at least two hydroxy groups; and

polymer (FH*) is a polymer comprising a partially fluorinated polyether backbone having two chain ends, wherein
each of said chain ends comprises a group selected from hydroxy group, allyl group or vinyl group; and
said backbone complies with structure (R FH -I):
—[CF 2 CFH(CF 2 ) z OR CF O(CF 2 ) z* CFHCF 2 —OR H O] y —  (R FH -I)

wherein
each of z and z* is independently 0 or 1;
R CF is a perfluoro alkylene chain comprising from 1 to 20 carbon atoms and optionally interrupted by one or more oxygen atoms;
R H is a linear or branched alkylene chain comprising from 2 to 12 carbon atoms, said alkyl chain optionally comprising one or more fluorine atoms and optionally being interrupted by one or more oxygen atoms; and
y is an integer, such that the average number molecular weight of the backbone of said polymer (FH) as determined by NMR analysis is from 306 to 50000.

7. The process according to claim 6 , wherein said polymer (FH*) complies with formula (FH b1 ):
CF 2 ═CF(CF 2 ) z OR CF O(CF 2 ) z* CFHCF 2 —OR H O—[CF 2 CFH(CF 2 ) z OR CF O(CF 2 ) z* CFHCF 2

—OR H O] y —CF 2 CFH(CF 2 ) z OR CF O(CF 2 ) z* CF═CF 2

wherein
each of z and z* is independently 0 or 1;
R CF is a perfluoro alkylene chain comprising from 1 to 20 carbon atoms and optionally interrupted by one or more oxygen atoms;
R H is a linear or branched alkylene chain comprising from 2 to 12 carbon atoms, said alkyl chain optionally comprising one or more fluorine atoms and optionally being interrupted by one or more oxygen atoms; and
y is an integer, such that the average number molecular weight of the backbone of said polymer (FH) as determined by NMR analysis is from 306 to 50000.

8. A perfluoropolyether polymer (PFPE), said polymer (PFPE) comprising a perfluoropolyether backbone having two chain ends,
wherein:
each chain end comprises at least one group selected from —OC(═O)F and perfluorinated alkyl chain comprising from 2 to 3 carbon atoms and
said backbone complies with structure (R pf -I):
—[CF 2 CF 2 (CF 2 ) z OR CF O—(CF 2 ) z* CF 2 CF 2 —OR F O] y —  (R pf -I)

wherein
R CF is a perfluoro alkyl chain comprising from 1 to 20 optionally interrupted by one or more oxygen atoms;
R F is a perfluoro alkyl chain comprising from 2 to 12 carbon atoms, optionally interrupted by one or more oxygen atoms;
each of z and z* is independently 0 or 1; and
y is an integer, such that the average number molecular weight of the backbone of said polymer (PFPE) as determined by NMR analysis is from 414 to 70 000;

with the proviso that:
when both z and z* are 0, at least one of said moiety R CF and said moiety R F is different from —CF 2 CF 2 — and —CF 2 CF 2 CF 2 CF 2 —; and
when both z and z* are 1, at least one of moiety R CF and moiety R F is different from —CF 2 CF 2 CF 2

Assignees

• Solvay Specialty Polymers It

Inventors

• Monzani Cristiano
• Tortelli Vito
• Galimberti Marco
• Valsecchi Roberto
• Maccone Patrizia

Classifications

• C08G65/007 Primary

  containing fluorine · CPC title

• G11B5/71

  characterised by the lubricant · CPC title

• C10M107/38

  containing halogen · CPC title

• C08G65/3312

  acyclic · CPC title

• C08G65/3236

  Fluorine · CPC title