Fluorinated tensides

Patent metadata

Field	Value
Publication number	US-10464874-B2
Application number	US-201515120288-A
Country	US
Kind code	B2
Filing date	Feb 18, 2015
Priority date	Feb 21, 2014
Publication date	Nov 5, 2019
Grant date	Nov 5, 2019

Abstract

The present invention relates to novel compounds containing fluorinated end groups, to the use thereof as surface-active substances, and to compositions comprising these compounds.

First claim

The invention claimed is:

1. A compound of formula (I)
Z n spacerX x   (I)

where
Z is R f —CHF—CF 2 —Y—(CH 2 ) m —,
where R f is CF 3 —CF 2 — or CF 3 —CF 2 —CF 2 —, or

Z is
R f —O—CHF—CF 2 —Y—(CH 2 ) m — or
R f —O—(CF 2 ) 1-4 —CHF—CF 2 —Y—(CH 2 ) m — or
R f —O—(CF 2 ) 1-4 —O—CHF—CF 2 —Y—(CH 2 ) m — or
R f —O—(CF(CF 3 )—CF 2 ) 1-4 —CHF—CF 2 —Y—(CH 2 ) m — or
R f —O—(CF(CF 3 )—CF 2 ) 1-4 —O—CHF—CF 2 —Y—(CH 2 ) m — or
R f —O—(CF 2 —O) 1-4 —CHF—CF 2 —Y—(CH 2 ) m — or
R f —O—(CF 2 —CF 2 —O) 1-4 —CHF—CF 2 —Y—(CH 2 ) m — or
R f —O—(CF 2 —O) 1-4 —(CF 2 —CF 2 —O) 1-4 —CHF—CF 2 —Y—(CH 2 ) m —,
where R f is CF 3 — or CF 3 —CF 2 — or CF 3 —CF 2 —CF 2 —,

n is 2 or 3,
Y is O or S,
m is 0 or 1,
spacer is a saturated branched or unbranched hydrocarbon unit, optionally containing heteroatoms,
X is —SO 3 − , —OSO 3 − , —COO − , —PO 3 2− , OPO 3 2− , —NR 1 R 2 R 3+ Z − , polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, —CH(OH)—CH 2 —NH-sach, —Y′—(CH 2 —CH 2 —O) v —R 4 , betaine, sulfo-betaine, —OH, —SH, —O-(glycoside) o′ , —S-(glycoside) o′ , —OCH 2 —CHOH—CH 2 —OH, —O CH 2 Ar(—NCO) p′ , —OAr(—NCO) p′ , amine oxide, or one of the following groups

and
wherein a counterion for an anionic group X may be present, which is a monovalent cation, H + , an alkali-metal cation or NR 4 + ,

R 1 , R 2 and R 3 are H,
Z is Cl − , Br − , I − , CH 3 SO 3 − , CF 3 SO 3 − , CH 3 PhSO 3 − or PhSO 3 − ,
R is, each independently H or C 1 -C 6 -alkyl,
u is an integer from the range from 1 to 6,
o′ is an integer from the range from 1 to 10,
p′ is 1 or 2,
Ar is an unsubstituted, mono- or polysubstituted aromatic ring or condensed ring system having 6 to 18 C atoms, in which one or two CH groups are optionally replaced by C═O,
glycoside is an etherified carbohydrate,
sach is a sugar,
Y′ is S, O or NH,
R 4 is H or alkyl,
v is 1-100, and
x is 1,
where all indices are selected so that no —O—O— bonds are present.

2. The compound according to claim 1 , wherein
spacer is a saturated, branched or linear hydrocarbon unit, and
Z is
R f —O—CHF—CF 2 —Y—(CH 2 ) m — or
R f —O—(CF 2 ) 1-4 —CHF—CF 2 —Y—(CH 2 ) m — or
R f —O—(CF 2 ) 1-4 —O—CHF—CF 2 —Y—(CH 2 ) m — or
R f —O—(CF(CF 3 )—CF 2 ) 1-4 —CHF—CF 2 —Y—(CH 2 ) m — or
R f —O—(CF(CF 3 )—CF 2 ) 1-4 —O—CHF—CF 2 —Y—(CH 2 ) m — or
R f —O—(CF 2 —O) 1-4 —CHF—CF 2 —Y—(CH 2 ) m — or
R f —O—(CF 2 —CF 2 —O) 1-4 —CHF—CF 2 —Y—(CH 2 ) m — or
R f —O—(CF 2 —O) 1-4 —(CF 2 —CF 2 —O) 1-4 —CHF—CF 2 —Y—(CH 2 ) m —.

3. The compound according to claim 1 , wherein
Z is
R f —O—CHF—CF 2 —Y—(CH 2 ) m — or
R f —O—(CF 2 ) 1-4 —CHF—CF 2 —Y—(CH 2 ) m — or
R f —O—(CF 2 ) 1-4 —O—CHF—CF 2 —Y—(CH 2 ) m —.

4. The compound according to claim 1 , wherein
Z is R f O—CHF—CF 2 —Y—(CH 2 ) m — or
R f —O—(CF 2 ) 1-4 —O—CHF—CF 2 —Y—(CH 2 ) m —.

5. The compound according to claim 1 , wherein
R f is CF 3 — or CF 3 —CF 2 —CF 2 —,
provided that, if Z is R f —CHF—CF 2 —Y—(CH 2 ) m —, then R f is CF 3 —CF 2 —CF 2 —.

6. The compound according to claim 1 , wherein
spacer-X is CR 5 (CH 2 ) n″ OH, CR 5 (CH 2 ) n″ SH, CR 5 (CH 2 ) n″ COOH, CR 5 (CH 2 ) n″ SO 3 H, CR 5 (CH 2 ) n″ NH 2 , CR 5 (CH 2 ) n″ NR′ 2 , CR 5 (CH 2 ) n″ —N + (CH 3 ) 3 Cl − , CR 5 (CH 2 ) n″ NR′ 2 —CH 2 —COO − , CR 5 (CH 2 ) n″ O(CHR a —CHR b O) n′″ R″, CR 5 (CH 2 ) n″ S(CHR a —CHR b O) n′″ R″ or CR 5 (CH 2 ) n″ NH(CHR a —CHR b O) n′″ R″,
n″ is 0 or 1,
n′″ is 1-30,
n is 2,
R 5 , R′ and R″ independently of one another are H or alkyl, and
R a and R b are H.

7. A compound, which is of formula (IIa) or (IIb):
[F(CF 2 ) n′ (O) o CHF—CF 2 —Y—(CH 2 ) m ] 2 spacer-X   formula (IIa)

[F(CF 2 ) n′ (O) o —(CF 2 ) 1-4 —O—CHF—CF 2 —Y—(CH 2 ) m ] 2 spacer-X   formula (IIb)

where
n′ is 1-6, provided that, if the compound is of the formula (IIa) and o is 0, then n′ is not 1,
m is 0 or 1,
o is 0 or 1,
Y is O or S,
spacer-X is —CR 5 (CH 2 ) n″ OH, CR 5 (CH 2 ) n″ SH, CR 5 (CH 2 ) n″ COOH, CR 5 (CH 2 ) n″ SO 3 H, CR 5 (CH 2 ) n″ NH 2 , CR 5 (CH 2 ) n″ NR′ 2 , CR 5 (CH 2 ) n″ N + (CH 3 ) 3 Cl − , CR 5 (CH 2 ) n″ NR′ 2 —CH 2 —COO − , CR 5 (CH 2 ) n″ O(CHR a —CHR b O) n′″ R″, CR 5 (CH 2 ) n″ S(CHR a —CHR b O) n′″ R″ or CR 5 (CH 2 ) n″ NH(CHR a —CHR b O) n′″ R″,
n″ is 0 or 1,
n′″ is 1-30, and
R 5 , R′ and R″ independently of one another are H or alkyl, and
R a and R b are H or alkyl.

8. The compound according to claim 7 , wherein, o is 1 and Y is O.

9. The compound according to claim 1 , which is of formula (III), (III′), (IV) or (IV′):

where
R f is CF 3 — or CF 3 —CF 2 — or CF 3 —CF 2 —CF 2 —, and
X is —SO 3 −, —OSO 3 − , —COO − , —PO 3 2− , OPO 3 2− , polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, —CH(OH)—CH 2 —NH-sach, —Y′—(CH 2 —CH 2 —O) v —R 4 , betaine, or sulfo-betaine.

10. The compound according to claim 1 , which is of formula (IIIa), (III′a), (IIIb), (III′b), (IVa), (IV′a), (IVb), (IV′b), (IVc) or (IV′c):

where
R a and R b are H,
n′″ is 1-30,
R″ is H or alkyl,
R f is CF 3 — or CF 3 —CF 2 — or CF 3 —CF 2 —CF 2 —, and
PEG stands for polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether or polypropylene glycol alkyl ether.

11. A compound, which is of formula (V), (VI), (VII), (VIII), (IX), (X), (XI) or (XII):

12. The compound according to claim 1 , wherein
spacer-X is CR 5 (CH 2 ) n″ OH, CR 5 (CH 2 ) n″ SH, CR 5 (CH 2 ) n″ COOH, CR 5 (CH 2 ) n″ SO 3 H, CR 5 (CH 2 ) n″ NH 2 , CR 5 (CH 2 ) n″ NR′ 2 , CR 5 (CH 2 ) n″ NR′ 2 —CH 2 —COO − , CR 5 (CH 2 ) n″ O(CHR a —CHR b O) n′″ R″, CR 5 (CH 2 ) n″ S(CHR a —CHR b O) n′″ R″or CR 5 (CH 2 ) n″ NH(CHR a —CHR b O) n′″ R″,
n″ is 0 or 1,
n′″ is 1-30,
R 5 , R′ and R″ independently of one another are H or alkyl, and
R a and R b are H.

13. The compound according to claim 1 , wherein X is amine oxide.

14. A composition comprising a compound according to claim 1 and a vehicle and optionally further active substances.

15. The composition according to claim 14 , which is selected from the group consisting of paints, coating preparations, fire-extinguishing compositions, lubricants, washing compositions, cleaning compositions, de-icers, developer solutions, wash solutions, photoresists for photolithographic processes, cosmetic products, agrochemicals, floor polishes, hydrophobicising compositions for textile finishing, and hydrophobicising compositions for glass treatment.

16. The composition according to claim 14 , which is selected from the group consisting of paints, coatings, printing inks, protective coatings, special coatings in electronic or optical applications, photoresists, top antireflective coatings, bottom antir

Assignees

• Merck Patent Gmbh

Inventors

• Friedrich Reiner
• Osthoff Julian

Classifications

• C07C309/10

  with the oxygen atom of at least one of the etherified hydroxy groups further bound to an acyclic carbon atom · CPC title

• C07C69/708

  Ethers · CPC title

• C07C229/12

  to carbon atoms of acyclic carbon skeletons · CPC title

• C07C217/28

  having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines · CPC title

• C07C59/135

  containing halogen · CPC title