# US 10,308,830 B2 · Fluoropolymer composition

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- Number: US 10,308,830 B2
- Document ID: US10308830B2
- Status: Granted
- Kind: B2
- Application number: 15/320,307
- Filed: 2015-06-16
- Published: 2017-05-25
- Granted: 2019-06-04
- Earliest claimed: 2014-06-19
- Assignees: Solvay Specialty Polymers Italy S.P.A.
- Applicants: Solvay Specialty Polymers Italy S.P.A.
- Inventors: Fabio Polastri; Valeriy Kapelyushko; Pasqua Colaianna
- Web page: https://patentgrep.com/patent/US10308830B2

## CPC

- C09D 127/18: Homopolymers or copolymers of tetrafluoroethene
- C08G 73/16: Polyester-imides
- C08L 27/18: Homopolymers or copolymers or tetrafluoroethene
- C08L 79/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C09D 179/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G 14/06: and monomers containing hydrogen attached to nitrogen
- C08L 61/34: Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

The invention pertains to a fluoropolymer composition comprising: —at least one fluoropolymer [polymer (A)]; —at least one benzoxazine compound [compound (B)] of formula (I), wherein each of Ra, equal to or different at each occurrence, is H or a C1-C12 alkyl group; Rb is a C1-C36 hydrocarbon group, possibly comprising heteroatoms, optionally comprising at least one benzoxazine group; j is zero or an integer of 1 to 4; each of Rc, equal or different at each occurrence, is a halogen or a C1-C36 hydrocarbon group, possibly comprising heteroatoms, optionally comprising at least one benzoxazine group; —at least one aromatic polyimide polymer [polymer (PI)]; —at least one organic solvent [solvent (S)], and to a method for coating a surface, specifically a metal surface, with a fluoropolymer, using said fluoropolymer composition.

## Claims

### Claim 1

A fluoropolymer composition comprising:
at least one fluoropolymer [polymer (A)];
at least one benzoxazine compound [compound (B)] of formula (I):
wherein each of Ra, equal to or different at each occurrence, is H or a C1-C12 alkyl group;
Rb is a C1-C36 hydrocarbon group, optionally comprising heteroatoms, optionally comprising at least one benzoxazine group; j is zero or an integer of 1 to 4;
and each of Rc, equal or different at each occurrence, is a halogen or a C1-C36 hydrocarbon group, optionally comprising heteroatoms, optionally comprising at least one benzoxazine group;
at least one aromatic polyimide polymer [polymer (PI)]; and
an organic solvent [solvent (S)].

### Claim 2 (depends on 1)

The fluoropolymer composition of claim 1, wherein solvent (S) is a solvent mixture [mixture (M)] comprising dimethylsulfoxide (DMSO) and at least one solvent selected from the group consisting of diesters of formula (Ide) and ester-amide of formula (Iea):
R1—OOC-Ade-COO—R2 (Ide)
R1—OOC-Aea-CO—NR3R4 (Tea)
wherein:
R1 and R2, equal to or different from each other, are independently selected from the group consisting of C1-C20 hydrocarbon groups;
R3 and R4, equal to or different from each other, are independently selected from the group consisting of hydrogen, C1-C36 hydrocarbon groups, optionally substituted, wherein R3 and R4 optionally form a cyclic moiety including the nitrogen atom to which they are bound, said cyclic moiety being optionally substituted and/or optionally comprising one or more than one additional heteroatom, and mixtures thereof;
Ade and Aea, equal to or different from each other, are independently a linear or branched divalent alkylene group.

### Claim 3 (depends on 1)

The fluoropolymer composition of claim 1, wherein the mixture (M) comprises, in addition to DMSO:
(i) at least one of the diester (I′de) and at least one diester (I″de), optionally in combination with at least one diester of formula (IIde); or
(ii) at least one of the esteramide (I′ea) and at least one esteramide (I″ea), optionally in combination with at least one esteramide of formula (IIea); or
(iii) combinations of (i) and (ii),
wherein:
(I′de) is R1—OOC-AMG-COO—R2
(I′ea) is R1—OOC-AMG-CO—NR3R4
(I″de) is R1—OOC-AES-COO—R2
(I″ea) is R1—OOC-AES-CO—NR3R4;
(IIea) is R1—OOC—(CH2)4—CO—NR3R4; and
(IIde) is R1—OOC—(CH2)4—COO—R2,
wherein:
AMG is of formula MGa —CH(CH3)—CH2—CH2— or MGb CH2—CH2—CH(CH3)—,
AES is of formula ESa —CH(C2H5)—CH2—, or ESb—CH2—CH(C2H5)—; and wherein R1 and R2, equal to or different from each other, are independently selected from the group consisting of C1-C20 alkyl, C1-C20 aryl, C1-C20 alkyaryl, C1-C20 arylalkyl groups;
R3 and R4, equal to or different from each other, are independently selected from the group consisting of C1-C20 alkyl, C1-C20 aryl, C1-C20 alkyaryl, C1-C20 arylalkyl groups, all said groups optionally comprising one or more than one substituent, optionally having one or more than one heteroatom, or wherein R3 and R4 form a cyclic moiety including and the nitrogen atom to which they are bound, said cyclic moiety optionally comprising one or more than one additional heteroatom.

### Claim 4 (depends on 1)

The fluoropolymer composition of claim 1, wherein mixture (M) comprises, in addition to DMSO:
(k) at least one of the diester (III4de), at least one diester (III3de), and at least one diester of formula (III2de);
(kk) at least one of the esteramide (III4ea), at least one esteramide (III3ea), and at least one esteramide of formula (III2ea); or
(kkk) combinations of (k) and (kk),
wherein:
(III4de) is R1—OOC—(CH2)4—COO—R2
(III3de) is R1—OOC—(CH2)3—COO—R2
(III2de) is R1—OOC—(CH2)2—COO—R2
(III4ea) is R1—OOC—(CH2)4—CO—NR3R4
(III3ea) is R1—OOC—(CH2)3—CO—NR3R4
(III2ea) is R1—OOC—(CH2)2—CO—NR3R4
wherein R1 and R2, equal to or different from each other, are independently C1-C20 alkyl, C1-C20 aryl, C1-C20 alkyaryl, C1-C20 arylalkyl groups;
R3 and R4, equal to or different from each other, are independently selected from the group consisting of C1-C20 alkyl, C1-C20 aryl, C1-C20 alkyaryl, C1-C20 arylalkyl groups, all said groups optionally comprising one or more than one substituent, optionally having one or more than one heteroatom, or wherein R3 and R4 form a cyclic moiety including the nitrogen atom to which they are bound, said cyclic moiety optionally comprising one or more than one additional heteroatom.

### Claim 5 (depends on 1)

The fluoropolymer composition of claim 1, wherein the polymer (A) is a per(halo)fluoropolymer selected from the group consisting of copolymers of tetrafluoroethylene (TFE) with at least one per(halo)fluoromonomer (PFM) different from TFE, said per(halo)fluoromonomer (PFM) being selected from the group consisting of:
C3-C8 perfluoroolefins;
C2-C6 perhalofluoroolefins comprising at least one halogen different from fluorine;
per(halo)fluoroalkylvinylethers complying with general formula CF2═CFORf1 in which Rf1 is a C1-C6 per(halo)fluoroalkyl, optionally comprising one or more than one halogen atom different from F;
per(halo)fluoro-oxyalkylvinylethers complying with general formula CF2═CFOX01, in which X01 is a C1-C12 per(halo)fluorooxyalkyl optionally comprising halogen atoms different from F, having one or more ether groups;
per(halo)fluoro-methoxy-alkylvinylethers complying with general formula CF2═CFOCF2ORf2 in which Rf2 is a C1-C6 per(halo)fluoroalkyl, optionally comprising halogen atoms different from F, or a C1-C6 per(halo)fluorooxyalkyl, optionally comprising halogen atoms different from F, having one or more ether groups;
per(halo)fluorodioxoles of formula:
wherein each of Rf3, Rf4, Rf5, Rf6, equal of different each other, is independently a fluorine atom, a C1-C6 per(halo)fluoroalkyl group, optionally comprising one or more oxygen atom, optionally comprising halogen atoms different from F.

### Claim 6 (depends on 4)

The fluoropolymer composition of claim 4, wherein the polymer (A) is selected from the group consisting of TFE copolymers comprising recurring units derived from hexafluoropropylene (HFP) and optionally from at least one perfluoroalkylvinylether complying with general formula CF2═CFORf1′ in which Rf1′ is a C1-C6 perfluoroalkyl.

### Claim 7 (depends on 4)

The fluoropolymer composition of claim 4, wherein polymer (A) is selected from the group consisting of TFE copolymers comprising recurring units derived from at least one per(halo)fluoroalkylvinylethers complying with general formula CF2═CFORf1 in which Rf1 is a C1-C6 per(halo)fluoroalkyl, optionally comprising one or more than one halogen atom different from F; and optionally further comprising recurring units derived from at least one C3-C8 perfluoroolefins.

### Claim 8 (depends on 1)

The fluoropolymer composition of claim 1, wherein polymer (PI) is a polyamideimide (PAT), said polyamideimide (PAT) being a polymer comprising more than 50% moles of recurring units comprising at least one aromatic ring, at least one imide group, as such and/or in its amic acid form, and at least one amide group which is not included in the amic acid form of an imide group [recurring units (RPAI)], said recurring units (RPAI) being selected from the group consisting of:
wherein:
Ar is a trivalent aromatic group;
R is a divalent aromatic group.

### Claim 9 (depends on 1)

The fluoropolymer composition of claim 1, wherein compound (B) complies with any of formulas (II), (III) and (IV) herein below:
wherein
RE is a covalent bond or a divalent group selected from the group consisting of —O—, —S—, —SO2—, —(CH2)m, with m being an integer from 1 to 6, —C(O)—, —C(CF3)2—, —(CF2)n, n being an integer from 1 to 6, and groups of formulas:
with
Y being a covalent bond or a divalent group selected from the group consisting of —O—, —S—, —SO2—, —(CH2)m, with m being an integer from 1 to 6, —C(O)—, —C(CF3)2—, —(CF2)n, n being an integer from 1 to 6;
RL is a divalent group selected from the group consisting of divalent C1-C12 aliphatic groups, linear or branched, or an aromatic group of formula:
with Z being a covalent bond or a divalent group selected from the group consisting of —O—, —S—, —SO2—, —(CH2)m, with m being an integer from 1 to 6, —C(O)—, —C(CF3)2—, —(CF2)n, n being an integer from 1 to 6;
j and j′, equal to or different from each other at each occurrence, is zero or is an integer of 1 to 3;
each of RG and RG′, equal or different at each occurrence, is a halogen or a C1-C36 hydrocarbon group, optionally comprising heteroatoms;
each of RF, equal to or different at each occurrence, is H or a C1-C12 alkyl group;
each of RH is a C1-C36 hydrocarbon group, optionally comprising heteroatoms.

### Claim 10 (depends on 9)

The composition according to claim 9, wherein compound (B) is selected from the group consisting of compounds (B-1) to (B-5) listed below:

### Claim 11 (depends on 1)

A process for manufacturing the fluoropolymer composition according to claim 1, the process comprising mixing polymer (A), polymer (P), mixture (M) and, when present, all other additional ingredients.

### Claim 12 (depends on 1)

A method for coating a surface, including a step of coating the composition according to claim 1 onto said surface, so as to obtain a wet coating layer on said surface.

### Claim 13 (depends on 12)

The method of claim 12, said method comprising a subsequent step of drying at temperatures ranging from room temperature to about 200° C., said wet coating layer, so as to obtain a dried coating layer onto said surface.

### Claim 14 (depends on 12)

The method of claim 12, wherein said dried coating layer is further coated with at least one additional layer of a fluoropolymer, so as to provide one or more than one outer fluoropolymer layer assembled onto the dried coating layer onto the surface.

### Claim 15 (depends on 8)

The fluoropolymer composition of claim 8, wherein Ar is a trivalent aromatic group selected from the group consisting of:
and corresponding optionally substituted structures, wherein X is selected from —O—, —C(O)—, —CH2—, —C(CF3)2—, and —(CF2)n—, and n is an integer from 1 to 5.

### Claim 16 (depends on 8)

The fluoropolymer composition of claim 8, wherein R is a divalent aromatic group selected from the group consisting of:
and corresponding optionally substituted structures, wherein Y is selected from —O—, —S—, —SO2—, —CH2—, —C(O)—, —C(CF3)2—, and —(CF2)n, and n is an integer from 0 to 5.