Fluorinated tensides

Patent metadata

Field	Value
Publication number	US-10315989-B2
Application number	US-201515120696-A
Country	US
Kind code	B2
Filing date	Feb 18, 2015
Priority date	Feb 21, 2014
Publication date	Jun 11, 2019
Grant date	Jun 11, 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 the formula (I′)
(ZC c D d ) n′ spacer m X x   (I′)

wherein
Z=R f —O—CHF—CF 2 —CR 1 R 2 —O— or
R f —O—(CF 2 ) 1-4 —CHF—CF 2 —CR 1 R 2 —O— or
R f —O—(CF 2 ) 1-4 —O—CHF—CF 2 —CR 1 R 2 —O— or
R f —O—(CF(CF 3 )—CF 2 ) 1-4 —CHF—CF 2 —CR 1 R 2 —O— or
R f —O—(CF(CF 3 )—CF 2 ) 1-4 —O—CHF—CF 2 —CR 1 R 2 —O— or
R f —O—(CF 2 —O) 1-4 —CHF—CF 2 —CR 1 R 2 —O— or
R f —O—(CF 2 —CF 2 —O) 1-4 —CHF—CF 2 —CR 1 R 2 —O— or
R f —O—(CF 2 —O) 1-4 —(CF 2 —CF 2 —O) 1-4 —CHF—CF 2 —CR 1 R 2 —O—,

n′=1, 2, 3, 4, 5 or 6,
R f =fluorinated alkyl, linear or branched,
R 1 =H or alkyl,
R 2 =H or alkyl,
C=−CR′ 2 —CR″ 2 —O—,
c=0 or an integer from the range from 1 to 100,
R′ and R″=independently of one another H or alkyl,
D=—CO—
d=0 or 1,
provided that at least one of c or d is not 0
spacer=a saturated or unsaturated, branched or unbranched hydrocarbon unit, optionally containing heteroatoms,
m=0 or 1,
X is a hydrophilic anionic, cationic, non-ionic or amphoteric group,
x=1, 2, 3 or 4.

2. A compound according to claim 1 , wherein n′ is equal to 2-3.

3. A compound according to claim 1 , wherein R f =fluorinated C1-C6-alkyl.

4. A compound according to claim 1 , wherein x=1.

5. A compound according to claim 1 , wherein Z is equal to:
R f —O—CHF—CF 2 —CR 1 R 2 —O— or
R f —O—(CF 2 ) 1-4 —CHF—CF 2 —CR 1 R 2 —O—
wherein R 1 and R 2 independently of one another ═H, —CH 3 or —CH 2 —CH 3 .

6. A compound of claim 1 , wherein Rf═CF 3 — or CF 3 —CF 2 — or CF 3 —CF 2 —CF 2 —.

7. A compound according to claim 1 , wherein the compound is of one of the formulae (II) to (XI) where:
Z is as defined in claim 1 ,
Y=Z optionally bonded through a —OCR″ 2 —CR′ 2 — group,
X′=Na + , K + , Li + , NH 4+ , or N(CH 3 ) 4+ ,
Q=Cl, Br, or I and
R′ and R″=independently of one another H or C1-C4 alkyl

8. A compound according to claim 7 , which is of one of the formulae (II-a), (II-b), (II-c) or (II-d):

9. A compound of claim 7 , characterised in that Y═Z optionally bonded through a —OCH 2 —CHR′ 2 group, wherein R′=H or C1-C2 alkyl.

10. A compound of claim 1 , wherein Rf═CF 3 -, CF 3 —CF 2 — or CF 3 —CF 2 —CF 2 —, Z=R f —O—CHF—CF 2 —CR 1 R 2 —O— or R f —O—(CF 2 ) 1-4 —CHF—CF 2 —CR 1 R 2 —O—, wherein R 1 and R 2 independently of one another =H, —CH 3 or —CH 2 —CH 3 and X is one of the groups —SO 3 − , —OSO 3 − , —PO 3 2− or OPO 3 2− , polyethylene glycol or polypropylene glycol, —CH(OH)—CH 2 —NH—Sach wherein Sach=a sugar, Y—(CH 2 —CH 2 —O) v —R 4 wherein Y in this formula=S, O or NH, R 4 =H or alkyl and v=1-100, betaine or sulfobetaine.

11. A compound of claim 1 , wherein R 1 =C1-C4 alkyl and R 2 =C1-C4 alkyl.

12. A compound of claim 1 , wherein R 1 =CH 3 or —CH 2 —CH 3 and R 2 =—CH 3 .

13. A compound according to claim 1 , wherein R f =fluorinated C1-C3-alkyl.

14. A compound according to claim 1 , wherein X is selected from the group consisting of anionic, cationic, nonionic and amphoteric groups:
wherein the anionic groups have one of the following anions with a counterion:
—COO − , —SO 3 − , —OSO 3 − , —PO 3 2− , —OPO 3 2− , —(OCH 2 CH 2 ) s —O—(CH 2 ) t —COO − , —(OCH 2 CH 2 ) s —O—(CH 2 ) t —SO 3 − , —(OCH 2 CH 2 ) s —O—(CH 2 ) t —OSO 3 − , —(OCH 2 CH 2 ) s —O—(CH 2 ) t —PO 3 2− , or —(OCH 2 CH 2 ) s —O—(CH 2 ) t -OPO 3 2− ;
or of the following formulae A, B or C,

wherein * marks the point of attachment of the X group, s is an integer of 1 to 1,000, t is an integer of 1, 2, 3 or 4 and w is an integer of 1, 2 or 3;

wherein the cationic groups are:
—NR 1 R 2 R 3+ Z − , —PR 1 R 2 R 3+ Z − , or one of the following formulae:

wherein * marks the point of attachment of the X group, R 1 , R 2 and R 3 each, independently of one another, are H, C 1-30 -alkyl, Ar or —CH 2 Ar wherein Ar is an unsubstituted or mono- or polysubstituted aromatic ring or condensed ring system having 6 to 18 C atoms, wherein one or two CH groups may be replaced by N, R is H or C 1-4 -alkyl in any ring position, and Z − is Cl − , Br − , I − , CH 3 SO 3 − , CF 3 SO 3 − , CH 3 PhSO 3 − , or PhSO 3 − ;

wherein the nonionic groups are:
linear or branched alkyl, wherein one or more non-adjacent C atoms have been replaced by O, S, and/or N;
—OH, —SH, —O-(glycoside) o′ , —S-(glycoside) o′ , —OCH 2 —CHOH—CH 2 —O H, —OCH 2 Ar(—NCO) p′ , —OAr(—NCO) p′ , or amine oxide, wherein o′ is an integer of 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, wherein one or two CH groups may be replaced by C═O and glycoside is an etherified carbohydrate;
one of the following formulae

wherein * marks the point of attachment of the X group, and u is an integer of 1 to 6;
or the group R 4 —(O—CH 2 CHR 5 ) m′ — wherein m″ is an integer of 1 to 100 and R 4 and R 5 are H or C 1-4 -alkyl;
or —CH(OH)—CH 2 —NH-Sach wherein Sach is a sugar;
or —Y—(CH 2 —CH 2 —O) v —R 4 wherein Y═S, O or NH, R 4 ═H or alkyl, and v=1-100; and

wherein the amphoteric groups are:
functional groups of the acetyldiamines, the N-alkylamino acids, the N-alkylaminosulfonic acids, the betaines or the sulfobetaines;
a group of one of the following formulae:

15. A method comprising adding a compound according to claim 1 as an additive to a composition selected from the group consisting of: paints, coatings, printing inks, protective coatings, special coatings in electronic or optical applications, photoresists, top antireflective coatings, bottom antireflective coatings, developer solutions and wash solutions and photoresists for photolithographic processes, cosmetic products, agrochemicals, floor polishes, photographic coatings and coatings of optical elements.

16. Composition comprising a compound according to claim 1 and a vehicle which is suitable for application in a: paint or coating preparation, fire-extinguishing composition, lubricant, washing or cleaning composition, de-icer, developer solution, rinse solution, immersion oil, photoresist for a photolithographic process, agrochemical, floor polish, cosmetic product, hydrophobicising composition for textile finishing or glass treatment or printing ink; and optionally further specific active substances.

17. Composition according to claim 16 , characterised in that the composition is selected from the group consisting of: paint and coating preparations, fire-extinguishing compositions, lubricants, washing and cleaning compositions, de-icers, developer solutions and wash solutions and photoresists for photolithographic processes, cosmetic products, agrochemicals, floor polishes and hydrophobicising compositions for textile finishing or glass treatment.

Assignees

• Merck Patent Gmbh

Inventors

• Friedrich Reiner
• Schooren Fanny

Classifications

• C07C309/17 Primary

  containing carboxyl groups bound to the carbon skeleton · CPC title

• C07C49/167

  containing only fluorine as halogen · CPC title

• C07C19/08

  containing fluorine · CPC title

• C07C43/04

  Saturated ethers · CPC title