Method of manufacturing cyclophosphazene derivatives

Patent metadata

Field	Value
Publication number	US-2016130289-A1
Application number	US-201414896048-A
Country	US
Kind code	A1
Filing date	Jun 3, 2014
Priority date	Jun 6, 2013
Publication date	May 12, 2016
Grant date	—

Abstract

A method of manufacturing cyclophosphazenes PFPE derivatives to be used in the lubrication of magnetic recording media is herein provided. The method comprises: a) a (per)fluoropolyether (PFPE) polyol [PFPE (P pol )] comprising a fluoropolyoxyalkylene chain (R f ) having two chain ends, each chain end comprising at least one hydroxy group, and b) the corresponding alkoxide of perfluoropolyether (P pol ) [PFPE (P alk )] wherein the equivalent concentration of PFPE (P alk ) in PFPE (P pol ) is lower than 30%, preferably ranging from 5% to 15%; 2) contacting mixture (M) with a perhalocyclophosphazene (CP halo ) to provide a mixture (M1) containing an equivalent ratio of PFPE (P alk )/(CP halo ) of at least 1; 3) allowing mixture (M1) to react until complete disappearance of P—Cl groups to provide a mixture (M2); 4) submitting mixture (M2) to hydrolysis to provide a mixture (M3); 5) optionally removing (P pol ) from mixture (M3) to provide a mixture (M4). A method of purifying mixture (M4) is also herein provided.

First claim

1 . A method of manufacturing cyclophosphazene derivatives, the method comprising:
contacting a mixture (M), the mixture (M) comprising:
a) a (per)fluoropolyether (PFPE) polyol [PFPE (P pol )] comprising a fluoropolyoxyalkylene chain (R f ) having two chain ends, each chain end comprising at least one hydroxy group, and
b) the corresponding alkoxide of perfluoropolyether (P pol ) [PFPE (P alk )], wherein the equivalent concentration of PFPE (P alk ) in PFPE (P pol ) is lower than 30% with a perhalocyclophosphazene (CP halo ) to provide a mixture (M1) containing an equivalent ratio of PFPE (P alk )/(CP halo ) of at least 1;
allowing mixture (M1) to react until complete disappearance of P—Cl groups to provide a mixture (M2); submitting mixture (M2) to hydrolysis to provide a mixture (M3); optionally removing PFPE (P pol ) from mixture (M3) to provide a mixture (M4).

2 . The method according to claim 1 wherein PFPE (P pol ) complies with formula (II):
Y—O—R f —Y′  (II)

wherein R f is a fully or partially fluorinated polyoxyalkylene chain comprising repeating units R°, said repeating units being selected from the group consisting of:
(i) —CFXO—, wherein X is F or CF 3 ,
(ii) —CFXCFXO—, wherein X, equal or different at each occurrence, is F or CF 3 , with the provision that at least one of X is —F,
(iii) —CF 2 CF 2 CW 2 O—, wherein each of W, equal or different from each other, are F, Cl, or H,
(iv) —CF 2 CF 2 CF 2 CF 2 O—,
(v) —(CF 2 ) j —CFZ-O— wherein j is an integer from 0 to 3 and Z is a group of general formula —OR f ′T 3 , wherein R f ′ is a fluoropolyoxyalkene chain comprising from 0 to 10 recurring units selected from: —CFXO—, —CF 2 CFXO—, —CF 2 CF 2 CF 2 O—, and —CF 2 CF 2 CF 2 CF 2 O—, with each of X being independently F or CF 3 and T 3 being a C 1 -C 3 perfluoroalkyl group; and
Y and Y′, equal to or different from one another, represent a hydrocarbon group containing at least one free hydroxy group, said hydrocarbon group being optionally fluorinated and/or optionally containing one or more heteroatoms.

3 . The method according to claim 2 wherein Y and Y′ are independently selected from:
—CFXCH 2 O(CH 2 CH 2 O) n H, —CFXCH 2 O(CH 2 CHCH 3 O) n H, and —CF 2 CF 2 CH 2 O(CH 2 CH 2 O) n H, wherein X is F or CF 3 and n ranges from 0 to 5;
—CFXCH 2 O(CH 2 CHOHCH 2 O) n′ H and —CF 2 CF 2 CH 2 O(CH 2 CHOHCH 2 O) n′ H, wherein X is F or CF 3 and n′ ranges from 1 to 3.

4 . The method according to claim 2 wherein chain R f complies with formula (R f -III):
—(CF 2 CF 2 O) a1 (CF 2 O) a2 —  (Rf-III)

wherein a1 and a2 are integers >0 such that the number average molecular weight is between 400 and 10,000, with the ratio a2/a1 being comprised between 0.1 and 10; and
Y and Y′, equal to or different from one another, are selected from:
—CFXCH 2 O(CH 2 CH 2 O) n H and —CF 2 CF 2 CH 2 O(CH 2 CH 2 O) n H, wherein X is F or CF 3 and n ranges from 0 to 5;
—CFXCH 2 O(CH 2 CHOHCH 2 O) n′ H and —CF 2 CF 2 CH 2 O(CH 2 CHOHCH 2 O) n′ H, wherein X is F or CF 3 and n′ ranges from 1 to 3.

5 . The method according to claim 4 wherein PFPE (P pol ) is a PFPE diol (P diol ) (IIA) wherein both Y and Y′ comply with formula —CF 2 CH 2 O(CH 2 CH 2 O) n H wherein n ranges from 0 to 2.

6 . The method according to claim 4 wherein PFPE (P pol ) is a mixture of:
PFPE diol (P diol ) (IIA), wherein both Y and Y′ comply with formula —CF 2 CH 2 O(CH 2 CH 2 O) n H wherein n ranges from 0 to 2;
PFPE tetraol (P tetraol )-(IIB), wherein both Y and Y′ comply with formula —CF 2 CH 2 OCH 2 CHOHCH 2 OH and
PFPE triol (P triol ) (IIC), wherein one of Y and Y′ is a group of formula —CF 2 CH 2 O(CH 2 CH 2 O) n H wherein n ranges from 0 to 2 and the other of Y and Y′ is a group of formula —CF 2 CH 2 OCH 2 CHOHCH 2 OH said mixture of PFPE (P pol ) (IIA)-(IIC) being optionally in the protected form.

7 . The method according to claim 1 wherein perhalocyclophosphazene (CP halo ) is selected from one or more of perhalocyclophosphazene (CP halo ) complying with formula (I-A) or (I-B):

wherein Hal is a halogen selected from fluorine, chlorine, bromine and iodine.

8 . The method according to claim 1 wherein the equivalent ratio of (PFPE-P alk )/(CP halo ) ranges from 1.1 to 2.5.

9 . The method according to claim 8 wherein the equivalent ratio of (PFPE-P alk )/(CP halo ) is 2 and wherein the equivalent concentration of (PFPE-P alk ) in (CP halo ) is between 5% and 15%.

10 . The method according to claim 1 further comprising submitting mixture (M4) fractionation with a supercritical fluid.

11 . A mixture of cyclophosphazene derivatives complying with formulae (CP-1)-(CP 4):

wherein R f is a fluoropolyoxyalkylene chain;
z is 3 or 4, w is selected from 0, 1 or 2; and
T and T′, equal to or different from one another, represent a hydrocarbon group which is optionally fluorinated and which optionally contains one or more heteroatoms and/or one or more hydroxy groups and a PFPE (P pol ) of formula (II) as defined in claim 2 .

12 . The mixture of cyclophosphazene derivatives according to claim 11 , wherein the mixture comprises the cyclophosphazene complying with formulae (CP-1)-(CP 3), characterised by a molar content of cyclophosphazene derivative (CP-1) of at least 40%.

13 . A cyclophosphazene derivative (CP-4) having formula:

wherein R f is a fluoropolyoxyalkylene chain;
z is 3 or 4, w is selected from 0, 1 or 2; and
T and T′, equal to or different from one another, represent a hydrocarbon group which is optionally fluorinated and which optionally contains one or more heteroatoms and/or one or more hydroxy groups and a PFPE (P pol ) of formula (II) as defined in claim 2 .

14 . A lubricant composition comprising a mixture of cyclophosphazene derivatives according to claim 11 in admixture with further ingredients or additives.

15 . A method of lubrifying magnetic recording media comprising contacting the media with a lubricant composition as defined in claim 14 .

16 . A lubricant composition comprising a cyclophosphazene derivative (CP-4) as defined in claim 13 in admixture with further ingredients or additives.

17 . A method of lubrifying magnetic recording media comprising contacting the media with a lubricant composition as defined in claim 16 .

18 . The method according to claim 4 wherein a1 and a2 are integers >0 such that the number average molecular weight is between 400 and 5,000, with the ratio a2/a1 being comprised between 0.2 and 5.

Assignees

• Solvay Specialty Polymers It

Inventors

• Valsecchi Roberto
• Picozzi Rosaldo
• Guarda Pier Antonio

Classifications

• C07F9/65815 Primary

  n = 3 · CPC title

• C10M105/74

  containing phosphorus · CPC title

• G11B5/7257

  Perfluoropolyether lubricant · CPC title

• C08G65/007

  containing fluorine · CPC title

• C08G65/337

  containing other elements (organic compounds containing halogens only as halides of a carboxyl group C08G65/332) · CPC title