Granted Patent B2

US 12,252,583 · App. 17/251,527 · Granted Mar 18, 2025

Inventors: Giovanni Fontana (Paderno Dugnano, IT); Marco Galimberti (Bollate, IT); Vito Tortelli (Milan, IT)

Assignee: SOLVAY SPECIALTY POLYMERS ITALY S.P.A.

C08G65/007C08G65/3322C08G2650/48

Abstract

Claims (77)

1. A method for the synthesis of a mixture of polymers said polymers comprising a partially fluorinated polyether backbone possessing a plurality of recurring units including at least one cyclic group; said process comprising:

Step (I): a step of contacting:

at least one fluorinated compound comprising at least two acyl-fluoride groups; and

at least one hydrogenated compound comprising at least two fluoroformate groups of formula —CR H 1 R H 2 —O—C(O)F, wherein each of R H 1 and R H 2 , equal to or different from each other at each occurrence, is independently H or a C1-C6 hydrocarbon group, in the presence of at least one fluoride-containing compound, wherein:

(i) at least one compound (F) is a compound (F C ) of formula:

F—C(═O)-Ef-Rcf-Ef-C(═O)—F

wherein:

 each of Ef, equal to or different from each other, is a bond, or a divalent fluorocarbon group, possibly comprising one or more than one heteroatoms selected from Cl, N, O and S;

Rcf is a divalent fluorocarbon cyclic group, which may be a cycloaliphatic or a cycloaromatic group, which may comprise one or more than one cyclic moiety, and which may comprise one or more than one heteroatom included in the cycle, said heteroatom being selected from N, O and S;

and/or

(ii) at least one compound (H) is a compound (H C ) of formula:

F—C(═O)O—CR H 1 R H 2 -EH C -RH C -EH C -CR H 1 -R H 2 —OC(═O)—F

wherein:

 each of EH C is selected from a bond, a —O— group and a divalent linear or branched (oxy)alkylene group, wherein said (oxy)alkylene group comprises from 1 to 8 carbon atoms and is optionally interrupted by one or more than one ethereal oxygen atom;

 RH C is divalent hydrocarbon cyclic group, which may be a cycloaliphatic or a cycloaromatic group, which may comprise one or more than one cyclic moiety, and which may comprise one or more than one heteroatom included in the cycle, said heteroatom being selected from N, O and S;

each of R H 1 and R H 2 , equal to or different from each other at each occurrence, is independently H or a C1-C6 hydrocarbon group;

to provide a polymer mixture (FH cyclic );

Step (II):

heating said polymer (FH cyclic ) obtained in Step (I) at a temperature exceeding 120° C., for a duration of at least 4 hours and in the presence of a fluoride-containing compound comprising at least one of (i) a metal fluoride of formula MeF y , with Me being a metal having y valence, y being 1 or 2, selected from the group consisting of NaF, CaF 2 , AgF, RbF, CsF, KF, and combinations thereof; and (ii) an (alkyl)ammonium fluoride of formula NR HN 4 F, with each of R HN , equal to or different from each other being, independently, a H or an alkyl group,

so effecting the thermolysis of at least a fraction of the chain ends of polymer (FH cyclic ) of formula —CR H 1 R H 2 —OC(═O)F to groups —CR H 1 R H 2 —F,

to provide polymer mixture (FH cyclic_CH2F );

Step (III A ):

reacting polymer mixture (FH cyclic_CH2F ) under esterification conditions in the presence of an alcohol of formula R h OH, with R h being a C 1 -C 3 hydrocarbon group; to provide for polymer mixture (FH cyclic_CH2F-ester/carbonate ), and then

Step (III):

fluorinating polymer mixture (FH cyclic_CH2F-ester/carbonate ) to provide for corresponding fluorinated polymer mixture (FF cyclic_CF3-ester/carbonate ).

2. The method of claim 1

wherein if compound F is not F C , compound F is selected from the group consisting of:

(F-i) FC(O)—CF 2 —C(O)F;

(F-ii) FC(O)—CF 2 —CF 2 —C(O)F;

(F-iii) FC(O)—CF 2 —CF 2 —CF 2 —C(O)F;

(F-iv) FC(O)—CF 2 —CF 2 —CF 2 —CF 2 —C(O)F; and

(F-v) FC(O)—CF 2 —O—CF 2 —C(O)F.

3. The method of claim 1 , wherein at least one compound (H) is a compound (H C ), and said compound (H C ) is reacted with one or more than one of the following:

(F-i) FC(O)—CF 2 —C(O)F;

(F-ii) FC(O)—CF 2 —CF 2 —C(O)F;

(F-iii) FC(O)—CF 2 —CF 2 —CF 2 —C(O)F;

(F-iv) FC(O)—CF 2 —CF 2 —CF 2 —CF 2 —C(O)F; and

(F-v) FC(O)—CF 2 —O—CF 2 —C(O)F.

4. The method of claim 1 , wherein compound (H C ) is an alicyclic compound of formula:

F—C(═O)O—CR H 1 R H 2 -RaliH C —CR H 1 R H 2 —OC(═O)—F,

wherein R H 1 and R H 2 have the meaning described above, and RaliH C is a divalent C5-C18 cycloaliphatic group, which is selected from the group consisting of:

divalent cyclobutylene groups;

divalent cyclopentylene groups;

divalent cyclohexylene groups;

divalent norbornylene groups;

divalent bicyclo[4.4.0]decyl groups;

divalent spiro[5,4]decyl groups; and

divalent spiro[5,5]undecyl groups; or an aromatic compound of formula:

F—C(═O)O—CR H 1 R H 2 —R aromHc —CR H 1 R H 2 —OC(═O)—F,

wherein R H 1 and R H 2 have the meaning described above, and RamHc is a divalent C 5 -C 18 cycloaromatic group, which may be selected from groups including one or more than one:

divalent benzylene groups;

divalent naphthylene groups;

divalent furylene groups;

divalent pyridylene groups;

divalent pyrrolylene groups;

divalent thiophenylene groups;

divalent aromatic groups of formula —Ar 1 —[W Ar —Ar 2 ] nar —, wherein each of Ar1 and Ar2 are divalent aromatic groups, W Ar is a bond or is a group of any of formula —O—, —C(CH 3 ) 2 —, —SO 2 —; —C(O)—; and nar is zero or an integer of 1 to 3.

5. The method of claim 4 , wherein compound (H C ) is selected from the group consisting of:

1,2-cyclobutanediol difluoroformate;

1,3-cyclobutanediol difluoroformate;

2,2,4,4-tetramethyl-1,3-cyclobutanediol difluoroformate;

1,1-cyclobutanedimethanol difluoroformate;

cis- and trans-1,2-cyclohexanediol difluoroformate;

1,4-cyclohexanediol difluoroformate;

cis- and trans-1,3-cyclohexanediol difluoroformate;

1,4-cyclohexanedimethanol difluoroformate;

4-methyl-1,2-cyclohexanedimethanol difluoroformate.

6. The method of claim 1 , wherein substantially all hydrogen atoms of moieties —CR H 1 R H 2 -E Hc -R Hc -E Hc -CR H 1 R H 2 —, and -E f -R cf -E f - are replaced in Step (III) with fluorine atoms, so that said moieties are transformed into groups of formula —C F 1 R F 2 -E FC -R FC -E FC -CR F 1 R F 2 —, and -E fF -R cfF -E fF - wherein:

each of E FC is selected from a bond, a —O— group and a divalent linear or branched perfluoro(oxy)alkylene group, wherein said perfluoro(oxy)alkylene group comprises from 1 to 8 carbon atoms and is optionally interrupted by one or more than one ethereal oxygen atom;

R FC is divalent perfluorocarbon cyclic group, which may be a cycloaliphatic or a cycloaromatic group, which may comprise one or more than one cyclic moiety, and which may comprise one or more than one heteroatom included in the cycle, said heteroatom being selected from N, O and S; and

each of R F 1 and R F 2 , equal to or different from each other, is independently F or a C 1 -C 6 perfluorocarbon group;

R cfF is a divalent perfluorocarbon cyclic group, which may be a perfluorocycloaliphatic, which may comprise one or more than one cyclic moiety, and which may comprise one or more than one oxygen atom included in the cycle;

each of E fF , equal to or different from each other, is a bond, or a divalent perfluorocarbon group, possibly comprising one or more than one heteroatoms selected from Cl, and O.

7. The method of claim 1 , wherein any of polymer mixtures (FH cyclic ), (FH cyclic_CH2F ), (FH cyclic_CH2F-ester-carbonate ), and (FF cyclic_CF3-ester-carbonate ) is further modified using:

(i) reactivity of —C(O)F and/or

(ii) reactivity of —O—C(O)—F groups,

to create different chain ends and/or is submitted to a variety of additional separation steps, so as to isolate specific components thereof.

Assignments (1)

Priority Claims (1)

Continuity (1)

References Cited (12)