Cyclophosphazene derivatives

Patent metadata

Field	Value
Publication number	US-10550226-B2
Application number	US-201515510559-A
Country	US
Kind code	B2
Filing date	Sep 8, 2015
Priority date	Sep 10, 2014
Publication date	Feb 4, 2020
Grant date	Feb 4, 2020

Abstract

The present invention relates to a phosphazene compound [compound (L)] comprising a cyclophosphazene central core wherein each phosphorus atom of said core bears a substituent independently selected from: a) a chain (A), said chain (A) comprising a (per)fluoropolyether chain [chain (Rf)], one or more aromatic or heteroaromatic moieties [moiety/ies (Arm)] and, optionally, one or more hydroxy groups and b) a chain (B), said chain (B) comprising a (per)fluoropolyether chain [chain (Rf)] and one or more hydroxy groups with the proviso that at least one phosphorous atom of the central core is substituted with chain (A) and to mixtures of compounds (L). The invention further relates to methods for preparing compounds (L), to lubricant compositions comprising compounds (L) and to methods for lubricating magnetic recording media comprising applying a compound (L) or a lubricant compositions containing them to the surface of said medium.

First claim

The invention claimed is:

1. A compound (L) comprising a cyclophosphazene central core wherein each phosphorus atom of said core bears substituents independently selected from:
a) a chain (A), said chain (A) comprising a (per)fluoropolyether chain [chain (R f )], one or more aromatic or heteroaromatic moieties [moiety/ies (Ar m )] and, optionally, one or more hydroxy groups and
b) a chain (B), said chain (B) comprising a (per)fluoropolyether chain [chain (R f )] and one or more hydroxy groups;
with the proviso that at least one phosphorous atom of the central core is substituted with chain (A);
wherein compound (L) is a compound of formula (L-1) below:

wherein:
x and y are 0, 1 or 2, with the proviso that x+y=2;
z is an integer of at least 3;
chain (A) complies with formula (A-1) below:
-G*-O—R f -E*  (A-1)

wherein:
G* is is selected from formulae (i*) (vii*) below:
—(OCH 2 CH 2 ) n OCH 2 XFC—;  (i*)

—[OCH(CH 3 )CH 2 )] n OCH 2 XFC—;  (ii*)

—(OCH 2 CH 2 ) n OCH 2 CF 2 CF 2 —;  (iii*)

—[OCH 2 CH(OH)CH 2 ] n′ OCH 2 XFC—;  (iv*)

—[OCH(CH 2 OH)CH 2 ] n′ OCH 2 XFC—;  (v*)

—[OCH 2 CH(OH)CH 2 ) n′ OCH 2 CF 2 CF 2 —; and  (vi*)

—[OCH(CH 2 OH)CH 2 ] n′ OCH 2 CF 2 CF 2 —  (vii*)

wherein X is F or CF 3 , n ranges from 0 to 5 and n′ ranges from 1 to 3;

(E*) is selected from formulae (viii*)-(xii*) below:
—CFXCH 2 O(CH 2 CH 2 O) n (CH 2 ) p Ar m ;  (viii*)

—CFXCH 2 O[CH 2 CH(CH 3 )O] n (CH 2 ) p Ar m ;  (ix*)

—CF 2 CF 2 CH 2 O(CH 2 CH 2 O) n (CH 2 ) p Ar m ;  (x*)

—CFXCH 2 O[CH 2 CH(OH)CH 2 O] n′ (CH 2 ) p Ar m and  (xi*)

—CF 2 CF 2 CH 2 O[CH 2 CH(OH)CH 2 O] n′ (CH 2 ) p Ar m ,  (xii*)

wherein X is F or CF 3 , n and n′ are as defined above, p is 0 or 1 and (Ar m ) is an aromatic or heteroaromatic moiety; and

R f is a (per)fluoropolyether chain;
and wherein either (G*) or (E*) comprises the one or more aromatic or heteroaromatic moiety (Ar m );

chain (B) complies with formula (B-1) below:
-G**-O—R f -E**  (B-1)

wherein:
G** is selected from formulae (i*) (vii*) below:
—(OCH 2 CH 2 ) n OCH 2 XFC—;  (i*)

—[OCH(CH 3 )CH 2 )] n OCH 2 XFC—;  (ii*)

—(OCH 2 CH 2 ) n OCH 2 CF 2 CF 2 —;  (iii*)

—[OCH 2 CH(OH)CH 2 ] n′ OCH 2 XFC—;  (iv*)

—[OCH(CH 2 OH)CH 2 ] n′ OCH 2 XFC—;  (v*)

—[OCH 2 CH(OH)CH 2 ) n′ OCH 2 CF 2 CF 2 —; and  (vi*)

—[OCH(CH 2 OH)CH 2 ] n′ OCH 2 CF 2 CF 2 —  (vii*)

wherein X is F or CF 3 , n ranges from 0 to 5 and n′ ranges from 1 to 3;

(E**) is selected from formulae (viii**)-(xii**) below:
—CFXCH 2 O(CH 2 CH 2 O) n H;  (viii**)

—CFXCH 2 O[CH 2 CH(CH 3 )O] n H;  (ix**)

—CF 2 CF 2 CH 2 O(CH 2 CH 2 O) n H;  (x**)

—CFXCH 2 O[CH 2 CH(OH)CH 2 O] n′ H and  (xi**)

—CF 2 CF 2 CH 2 O[CH 2 CH(OH)CH 2 O] n′ H,  (xii**)

wherein X is F or CF 3 and n and n′ are as defined above; and

R f is a (per)fluoropolyether chain.

2. The compound according to claim 1 wherein chain (R f ) in chains (A) and (B) is a fully or partially fluorinated polyoxyalkylene chain that comprises repeating units R ∘ , said repeating units being independently 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 proviso 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, H,
(iv) —CF 2 CF 2 CF 2 CF 2 O—, and
(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, wherein R f ′ is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being selected from: —CFXO—, —CF 2 CFXO—, —CF 2 CF 2 CF 2 O—, —CF 2 CF 2 CF 2 CF 2 O—, with each of each of X being independently F or CF 3 and T being a C 1 -C 3 perfluoroalkyl group.

3. The compound according to claim 2 wherein chain (R f ) complies with formula (R f -III) here below:
—(CF 2 CF 2 O) a1 (CF 2 O) a2 —  (R f -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.

4. The compound according to claim 1 wherein z is 3 or 4.

5. The compound according to claim 1 wherein (Ar m ) is phenyl or pyridyl bearing one or more substituents independently selected from fluorine, trifluoromethyl and nitro.

6. The compound according to claim 1 wherein:
(G*) and (G**) are selected from:
formula (i*) —(OCH 2 CH 2 ) n OCH 2 XFC—, wherein X is F and n is selected from 0, 1 and 2; and
formula (iv*) —[OCH 2 CH(OH)CH 2 ] n′ OCH 2 XFC—, wherein X is F and n′ is (E*) is selected from:
formula (viii*) —CFXCH 2 O(CH 2 CH 2 O) n (CH 2 ) p Ar m , wherein X is F, n is selected from 0, 1 and 2, p is 0 and (Ar m ) is phenyl or pyridyl bearing one or more substituents independently selected from fluorine, trifluoromethyl and nitro; and
formula (xi*) —CFXCH 2 O[CH 2 CH(OH)CH 2 O] n′ (CH 2 ) p Ar m , wherein X is F, n′ is 1, p is 0 and (Ar m ) is phenyl or pyridyl bearing one or more substituents independently selected from fluorine, trifluoromethyl and nitro;

and (E**) is selected from
formula (viii**) —CFXCH 2 O(CH 2 CH 2 O) n H, wherein X is F and n is selected from 0, 1 and 2; and
formula (xi**) —CFXCH 2 O[CH 2 CH(OH)CH 2 O] n′ H, wherein X is F and n′ is 1.

7. A mixture comprising a compound of claim 1 and one or more compounds comprising a cyclophosphazene central core wherein each phosphorus atom of said core bears substituents independently selected from:
a) a chain (A), said chain (A) comprising a (per)fluoropolyether chain [chain (R f )], one or more aromatic or heteroaromatic moieties (Ar m ) and, optionally, one or more hydroxy groups and
b) a chain (B), said chain (B) comprising a (per)fluoropolyether chain [chain (R f )] and one or more hydroxy groups and
c) at least one chain (B′), said chain (B′) comprising a (per)fluoropolyether chain (R f ), wherein both ends of chain (R f ) are bound either to a same phosphorus atom of the cyclophosphazene ring or to two different phosphorus atoms of the cyclophosphazene ring via a bridging group (G), said group (G) comprising one or more aromatic or heteroatomatic moieties and/or one or more hydroxy groups,
with the proviso that at least one chain (A), or at least one chain (B′) wherein bridging group (G) comprises one or more aromatic or heteroaromatic moieties, (Ar m ) is present.

8. A lubricant composition comprising one or more compounds of claim 1 .

9. A method for lubricating sliding or moving parts of a magnetic recording medium comprising applying to said parts the composition of claim 8 .

10. A magnetic recording medium comprising a sliding or moving part having applied thereto the composition of claim 8 .

Assignees

• Solvay Specialty Polymers It

Inventors

• Valsecchi Roberto
• Mutta Fabrizio

Classifications

• C10N2040/18

  in connection with recordings on magnetic tape or disc · CPC title

• C07F9/65815

  n = 3 · CPC title

• C08G2650/48

  containing fluorine, e.g. perfluropolyethers · CPC title

• C10M107/38

  containing halogen · CPC title

• C10M2213/0606

  used as base material · CPC title