Process for the synthesis of (per)fluoropolyether amines

Patent metadata

Field	Value
Publication number	US-10723839-B2
Application number	US-201615743129-A
Country	US
Kind code	B2
Filing date	Jul 7, 2016
Priority date	Jul 9, 2015
Publication date	Jul 28, 2020
Grant date	Jul 28, 2020

Abstract

A process for the manufacture of a (per)fluoropolyether amine comprising reacting a sulfonic ester of a (per)fluoropolyether alcohol with an excess of ammonia or organic amine at selected temperature is herein disclosed. The process allows obtaining (per)fluoropolyether amines, in particular primary, secondary and tertiary (per)fluoropolyether amines with high yields and selectivity and can be conveniently applied on an industrial scale.

First claim

The invention claimed is:

1. A process for the manufacture of a (per)fluoropolyether amine, said process comprising reacting a sulfonic ester of a (per)fluoropolyether alcohol with an excess of ammonia or of organic amine at a temperature ranging from 20° C. to 50° C. and in the presence of an aprotic organic solvent selected from acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexafluoroxylene and mixtures thereof,
wherein the sulfonic ester of a (per)fluoropolyether alcohol complies with formula (I)
A-O—R f —B  (I)

wherein:
A is a group of formula —CFX—CH 2 —O—(CHYCHYO) n —SO 2 —R wherein: X is F or CF 3 ; R is perfluoroalkyl, each Y is, independently of each other, hydrogen or lower alkyl and n is 0 or a positive number;
R f is a fully or partially fluorinated polyether chain;
B is the same as A or is a (per)haloalkyl group.

2. The process according to claim 1 , wherein the sulfonic ester of the(per)fluoropolyether alcohol is a sulfonic ester of a polymer comprising a fully or partially fluorinated polyether chain (R f ) having at least two chain ends, wherein at least one chain end bears at least one hydroxy group and wherein at least one chain end bears at least one sulfonic ester group.

3. The process according to claim 2 , wherein the sulfonic ester of the(per)fluoropolyether alcohol is a sulfonic ester of a polymer comprising a fully or partially fluorinated polyether chain (R f ) having two chain ends, wherein at least one chain end bears at least one hydroxy group.

4. The process according to claim 1 , wherein chain (R f ) comprises recurring units)(R o ) selected from:
(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, is F, Cl, or 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 each independently being chosen 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 each of X being independently F or CF 3 and T being a C 1 -C 3 perfluoroalkyl group.

5. The process according to claim 4 , wherein chain (R f ) complies with formula (R f -I):
—(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF 2 CF 2 CF 2 O) g3 (CF 2 CF 2 CF 2 CF 2 O) g4 —  (R f -I)

wherein:
each X 1 is independently selected from —F and —CF 3 ;
each X 2 and X 3 , equal or different from each other and at each occurrence, are independently —F, —CF 3 , with the proviso that at least one of X is —F;
g1, g2, g3, and g4, equal or different from each other, are independently integers≥0, such that g1+g2+g3+g4 is in the range from 2 to 300; should at least two of g1, g2, g3 and g4 be different from zero, the different recurring units are statistically distributed along the chain.

6. The process according to claim 5 , wherein g1+g2+g3+g4 is in the range from 2 to 100.

7. The process of claim 5 , wherein chain (R f ) is selected from chains of formulae (R f —IIA)-(R f -IIE):
—(CF 2 CF 2 O) a1 (CF 2 O) a2 —  (R f -IIA)

wherein:
a1 and a2 are independently integers≥0 such that the number average molecular weight is between 400 and 10,000;
—(CF 2 CF 2 O) b1 (CF 2 O) b2 (CF(CF 3 )O) b3 (CF 2 CF(CF 3 )O) b4 —  (R f -IIB)

wherein:
b1, b2, b3, and b4 are each independently integers≥0 such that the number average molecular weight is between 400 and 10,000;
—(CF 2 CF 2 O) c1 (CF 2 O) c2 (CF 2 (CF 2 ) cw CF 2 O) c3 —  (R f —IIC)

wherein:
cw is 1 or 2;
c1, c2, and c3 are independently integers≥0 such that the number average molecular weight is between 400 and 10,000;
—(CF 2 CF(CF 3 )O) d —  (R f —IID)

wherein:
d is an integer>0 such that the number average molecular weight is between 400 and 10,000; and
—(CF 2 CF 2 C(Hal) 2 O) e1 —(CF 2 CF 2 CH 2 O) e2 —(CF 2 CF 2 CH(Hal)O) e3 —  (R f —IIE)

wherein:
each Hal, equal or different at each occurrence, is a halogen selected from fluorine and chlorine atoms;
e1, e2, and e3, equal to or different from each other, are independently integers≥0 such that the (e1+e2+e3) sum is comprised between 2 and 300.

8. The process of claim 7 , wherein chain (R f ) complies with formula (R f -III):
—(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 4,000, with the ratio a2/a1 being comprised between 0.2 and 5.

9. The process according to claim 7 , wherein:
both a1 and a2 are different from zero, with the ratio a1/a2 being comprised between 0.1 and 10;
b1 is 0 and b2, b3 and b4 are each >0, with the ratio b4/(b2+b3) being ≥1; and
c1, c2 and c3 are all >0, with the ratio c3/(c1+c2) being less than 0.2.

10. The process of claim 1 , wherein the organic amine complies with formula (III-A):
HN(R 1 ) 2   (III-A)

wherein R′, equal to or different from one another, is:
hydrogen or a C 1 -C 20 straight or branched alkyl chain, said alkyl chain optionally comprising one or more mono- or polycyclic hydrocarbon moieties, heteroatoms other than nitrogen, or functional groups other than amine groups; or
an aromatic mono- or polycyclic hydrocarbon moiety comprising from 4 to 12 carbon atoms, said mono- or polycyclic hydrocarbon moiety optionally comprising heteroatoms or functional groups;
with the proviso that at least one R 1 is other than hydrogen and with the proviso that, if amine (III-A) is an aromatic monoamine, at least one R 1 is an aromatic mono- or polycyclic hydrocarbon moiety wherein at least one sp 2 carbon is bound to the nitrogen atom.

11. The process of claim 1 , wherein the organic amine complies with formula (III-B):

wherein:
R 2 , R 4 and R 6 , equal to or different from one another, are independently selected from: hydrogen; C 1 -C 20 straight or branched alkyl chains, said alkyl chains optionally comprising one or more mono- or polycyclic hydrocarbon moieties, heteroatoms other than nitrogen, or functional groups other than amine groups; and aromatic mono- or polycyclic hydrocarbon moieties comprising from 4 to 12 carbon atoms, said mono- or polycyclic hydrocarbon moieties optionally comprising heteroatoms or functional groups, with the proviso that at least one of R 2 , R 4 and R 6 is hydrogen;
R 3 and R 5 , equal to or different from one another, are independently selected from: straight or branched alkylene chains comprising from 1 to 20 carbon atoms, optionally comprising one or more mono- or polycyclic hydrocarbon moieties, heteroatoms other than nitrogen, or functional groups other than amine groups; and aromatic mono- or polycyclic hydrocarbon moieties comprising from 4 to 12 carbon atoms, said mono- or polycyclic hydrocarbon moieties, optionally comprising heteroatoms or functional groups; and
z is 0 or an integer equal to or higher than 1.

12. The process according to claim 11 , wherein z is 0 or an integer ranging from 1 to 3.

13. The process of claim 1 , wherein:
if ammonia or an organic monoamine is used, the excess of ammonia or organic amine is of at least 2 equivalents of ammonia or organic amine per equivalent of sulfonic ester of a (per)fluoropolyether alcohol;
if an organic polyamine is used, the ratio:
(E q Am)/(E q PFPE sulfonic

Assignees

• Solvay Specialty Polymers It

Inventors

• Tonelli Claudio Adolfo Pietro
• Wlassics Ivan Diego
• Marchionni Giuseppe

Classifications

• C08G65/33306 Primary

  acyclic · CPC title

• C08G2650/50

  containing nitrogen, e.g. polyetheramines or Jeffamines(r) · CPC title

• C08G65/007

  containing fluorine · CPC title

• C08G65/3255

  Ammonia · CPC title

• C08G2650/48

  containing fluorine, e.g. perfluropolyethers · CPC title