Fluorinated monomers comprising anthracene moieties

Related applications

[0001] This application claims priority to U.S. provisional application No. US 62/634,427, filed on February 23, 2018 and to European patent application No. EP 18161623.6, filed on March 13, 2018, the whole content of each of these applications being incorporated herein by reference for all purposes.

Technical Field

[0002] The present disclosure relates to fluorinated monomers comprising anthracene moieties, able to undergo a cycloaddition reaction under UV light. The present disclosure also relates to a process for manufacturing the fluorinated monomers. The present disclosure also relates to the adducts obtained from the fluorinated monomers, as well as to the process for preparing the adducts.

Background Art

[0003] Stimuli-responsive materials, also called sometimes smart polymers, are defined as materials which can change their properties under specific conditions, for example humidity, pH, UV light or heat. Stimuli-responsive polymers are for example used in drug delivery. As an example, conformational changes in water permeability under acid / basic pH conditions can be exploited to design carriers for drugs to be released at a desired body location. Stimuli-responsive polymers are also used in biomedical engineering. Smart polymers sensitive to UV light can be used, for example, as shape-memory materials for the manufacture of stents, as self-healing materials and for the manufacture of medical implants.

[0004] An object of the present invention is to provide a smart material which can undergo crosslinking or chain extension under specific conditions so as to generate a stable product, for the preparation of coatings, films and shaped articles in general.

[0005] Another object of the present invention is to provide a smart material which, when in the form of a crosslinked product or a chain extended product, can easily be recycled under specific conditions, without the need of chemicals.

Summary of invention

[0006] The present invention is directed to a fluorinated monomer comprising anthracene moieties. More precisely, the monomer is according to formula (la) or (lb):

T ^A -CF ₂ -R _fa -T ^A’ (la)

T ^A -CF ₂ -R _fb -T ^A’ (lb) wherein

- R _fa is a fluorinated (co)polymer;

- R _fb is a branched fluorinated (co)polymer, optionally comprising at least one group T ^A” ;

- T ^A , T ^A’ and T ^A ”, equal to or different from each other, are selected from the group consisting of:

(i) C ₁ -C ₂₄ (hydro)(fluoro)carbon groups, possibly comprising one or more than one of H, O, and Cl; and

(ii) (hydro)(fluoro)carbon groups comprising at least an anthracene moiety (anthracene group) of formula (II):

wherein

- R is a halogen atom or an alkyl group, optionally branched, preferably an C1-C18 alkyl group optionally substituted with one or several halogen atoms; and - n is 0 or an integer from 1 to 9, preferably 0;

with the proviso that at least one of T ^A , T ^A’ and T ^A ” comprises an anthracene moiety according to formula (II).

[0007] The present invention is also directed to a process for manufacturing the fluorinated monomer comprising anthracene moieties, possibly substituted with Rn as above defined.

[0008] The present invention is also directed to adducts obtained from exposing at least the monomers of the present invention to UV light at a wavelength ranging from 300 nm to 600 nm, as well as to the process to prepare these adducts.

[0009] The present invention is also directed to polymer blends comprising at least 1 mol.% of the monomers of the present invention.

Description of embodiments

[0010] The present invention relates to a monomer is according to formula (la) or (lb):

T ^A -CF ₂ -R _fa -T ^A’ (la)

T ^A -CF ₂ -R _fb -T ^A’ (lb)

wherein

- R _fa is a fluorinated (co)polymer;

- R _fb is a branched fluorinated (co)polymer, optionally comprising at least one group T ^A” ;

- T ^A , T ^A’ and T ^A ”, equal to or different from each other, are selected from the group consisting of:

(i) Ci-C ₂₄ (hydro)(fluoro)carbon groups, possibly comprising one or more than one of H, O, and Cl; and

(ii) (hydro)(fluoro)carbon groups comprising at least an anthracene moiety (anthracene group) of formula (II):

wherein - R is a halogen atom or an alkyl group, optionally branched, preferably an C1-C18 alkyl group optionally substituted with one or several halogen atoms; and

- n is 0 or an integer from 1 to 9, preferably 0;

with the proviso that at least one of T ^A , T ^A’ and T ^A ” comprises an anthracene moiety according to formula (II).

[0011] The new fluorinated monomers of the present invention comprise anthracene moieties, which are able to undergo adduct formation under certain stimuli. The reaction is induced by UV light and is reversible under different UV light frequencies. The reaction is also thermally reversible, for example microwave reversible.

[0012] These new monomers can be used to obtain films, coatings and shaped articles in general. Exposed to UV light, the monomers form adducts. As used herein, the term“adduct” means the addition product of at least two monomers of the present invention, with or without the elimination of a by- product. Adducts containing unreacted anthracene moieties can react further to form larger adducts. The so-obtained adducts can be degraded and recycled without the addition of other chemicals, but by selecting conditions to induce either complete or partial conversion of the adducts back into monomers or into smaller adducts.

[0013] According to the present invention, both R _fa and R¾ are fluorinated (co)polymers. R _fa is preferably a linear fluorinated (co)polymer. Monomers of formula (la) presents an anthracene functionality of 2 when both T ^A and T ^A’ consist in (hydro)(fluoro)carbon groups comprising at least an anthracene moiety (anthracene group) of formula (II). R¾ is a branched fluorinated (co)polymer. Monomers of formula (lb) presents an anthracene functionality which can be higher than 2, for example comprised between 2.1 and 6. Monomers of formula (lb) may, for example, present an anthracene functionality equal to 3 if, for example, T ^A , T ^A’ and T ^A” consist in (hydro)(fluoro)carbon groups comprising at least an anthracene moiety (anthracene group) of formula (II). Monomers of formula (lb) may also present an anthracene functionality higher then 3, if monomers of formula (lb) comprise more than three (hydro)(fluoro)carbon groups comprising at least an anthracene moiety (anthracene group) of formula (II). For example, monomers of formula (lb) may comprise four (hydro)(fluoro)carbon groups comprising at least an anthracene moiety (anthracene group) of formula (II). According to this example, the functionality of the monomers of formula may range between 0 and 4, preferably between 2 and 4, more preferably between 2.5 and 4.

[0014] Monomer of formula (I)

[0015] According to a first aspect of the invention, the present invention relates to a monomer of formula (I):

T ^A -CF ₂ -R _fa -T ^A’ (la)

T ^A -CF ₂ -R _fb -T ^A’ (lb)

wherein

- R _fa is a fluorinated (co)polymer;

- R _fb is a branched fluorinated (co)polymer, optionally comprising at least one group T ^A” ;

- T ^A , T ^A’ and T ^A ”, equal to or different from each other, are selected from the group consisting of:

(i) C1-C24 (hydro)(fluoro)carbon groups, possibly comprising one or more than one of H, O, and Cl; and

(ii) (hydro)(fluoro)carbon groups comprising at least an anthracene moiety (anthracene group) of formula (II):

wherein

- R is a halogen atom or an alkyl group, optionally branched, preferably an C1-C18 alkyl group optionally substituted with one or several halogen atoms; and

- n is 0 or an integer from 1 to 9, preferably 0;

with the proviso that at least one of T ^A , T ^A’ and T ^A ” comprises an anthracene moiety according to formula (II). [0016] According to an embodiment of the present invention, the monomer of the present invention is according to formula (Ilia) or (lllb):

T ^B -CF ₂ -R _fa -T ^B’ (Ilia)

T ^B -CF ₂ -R _fb -T ^B’ (lllb)

wherein

- R _fa is a fluorinated (co)polymer;

- R _fb is a branched fluorinated (co)polymer, optionally comprising at least one group T ^A” ;

- T ^B , T ^B’ and T ^B ”, equal to or different from each other, are selected from the group consisting of:

(i) a group of any of formulas -CF3, -CF ₂ CI, -CF ₂ CF3, -CF(CF3)2 _, -CF ₂ FI, -

CFH ₂ , -CF ₂ CH ₃ , -CF ₂ CHF _2J -CF ₂ CH ₂ F, -CFZ ^* CH ₂ OH, - CFZ*COOH, -CFZ*COORi and -CFZ*-CH ₂ (OCH ₂ CH ₂ ) _k -OH, wherein k is ranging from 0 to 10, wherein Z ^* is F or CF3; Ri is a C ₁ -C6 hydrocarbon chain; and

(ii) (hydro)(fluoro)carbon groups comprising at least an anthracene moiety

(anthracene group) of formula (II):

wherein

- R is a halogen atom or an alkyl group, optionally branched, preferably an C1-C18 alkyl group optionally substituted with one or several halogen atoms; and

- n is 0 or an integer from 1 to 9, preferably 0;

with the proviso that at least one of T ^B , T ^B’ and T ^B ” comprises an anthracene moiety according to formula (II).

[0017] According to an embodiment of the present invention, n in formula (II) equals 0.

[0018] According to an embodiment, the monomer has a number average molecular weight (Mn) ranging from 400 to 130,000 g/mol, preferably from 500 to 120,000 g/mol, even more preferably from 1 ,000 to 110,000 g/mol, as determined by NMR.

[0019] The monomers of the present invention may be provided as the reaction products of synthetic methods and raw materials used, as mixtures/blends of monomers (also called compounds). These monomers may for example comprise different chemical entities (e.g. differing because of the nature and length of the R _fa /R _fb chain), possibly comprising variable fractions of monomers wherein two (in the case of a linear structure), three or more (in the case of a branched structure) chain ends are (hydro)(fluoro)carbon groups comprising at least an anthracene moiety of formula (II) (i.e. difunctional compounds/monomers) and of monomers wherein only one chain end is (hydro)(fluoro)carbon groups comprising at least an anthracene moiety of formula (II) (i.e. monofunctional compounds/monomers), possibly associated with minor amounts of side products of similar structure, but wherein both of chain ends of the R _fa chain fails to be bound to anthracene moieties.

[0020] Regarding the proportion of monofunctional and difunctional monomers, good results have been achieved when the monomers consist of a major amount of monomers of formula (la) [T ^A -CF ₂ -R _fa -T ^A ’] as above detailed, wherein both T ^A and T ^A ’ are (hydro)(fluoro)carbon groups comprising at least an anthracene moiety of formula (II) (i.e. difunctional compounds/monomers), and a minor amount of monomers of formula (la) [T ^A -CF ₂ -R _fa -T ^A ’] as above detailed, wherein only one of T ^A and T ^A ’ is an (hydro)(fluoro)carbon group comprising at least an anthracene moiety of formula (II), the other group being free from the anthracene moiety (i.e. monofunctional compounds/monomers).

[0021] According to an embodiment of the present invention, the functionality of the monomer is greater than 1.7, preferably greater than 1.8, more preferably greater than 1.9.

[0022] Difunctional and monofunctional monomers may be separately and individually used in compositions. However, the monomers are generally a mixture of difunctional and monofunctional monomers. When the compound is provided as a mixture of difunctional and monofunctional monomers, the amount of difunctional monomers and monofunctional monomers may be such that the difunctional monomers are representative of at least 50 mol.%, preferably at least 55 mol.%, more preferably at least 60 mol.% of the blend of monomers. Alternatively, the amount of difunctional monomers and monofunctional monomers may be such that the monofunctional monomers are representative of at least 50 mol.%, preferably at least 55 mol.%, more preferably at least 60 mol.% of the blend of monomers.

[0023] The monomers of the present invention may be polyfunctional. They may also be provided as reaction products of synthetic methods and raw materials used, as mixtures/blends of monomers and consist of a major amount of monomers of formula (lb) [T ^A -CF ₂ -R _fb -T ^A ’] as above detailed, comprising more than two anthracene moieties according to formula (II). In this case, R¾ comprises at least two anthracene moieties according to formula (II). R¾ may for example comprise two, three, four or more anthracene moieties according to formula (II). When they are provided as reaction products, the blends may also comprise difunctional and monofunctional monomers, as described above, possibly associated with minor amounts of side products of similar structure, but wherein both of chain ends of the R¾ chain fails to be bound to anthracene moieties.

[0024] According to an embodiment of the present invention, the functionality of the monomer is greater than 2.0, preferably greater than 2.1 , more preferably greater than 2.2. The functionality of the monomer can for example be as high as 6 .

[0025] Polyfunctional monomers may be separately from difunctional and monofunctional monomers and individually used in compositions. However, the monomers are generally a mixture of polyfunctional, difunctional and monofunctional monomers. When the compound is provided as a mixture of polyfunctional, difunctional and monofunctional monomers, the amount of polyfunctional monomers, difunctional monomers and monofunctional monomers may be such that the polyfunctional monomers are representative of at least 50 mol.%, preferably at least 55 mol.%, more preferably at least 60 mol.% of the blend of monomers.

[0026] The monomers may be purified to remove side products. In that case, minor amounts of the side products (also called non-functional compounds) are not detrimental and may be tolerated.

[0027] The side products may be of formula (IVa) or (IVb):

W-CF ₂ -R _fa -W’ (IVa)

W-CF ₂ -R _fb -W’ (IVb)

wherein:

R _fa is a chain R _fa , as above detailed;

R _fa is a chain R _fb , as above detailed;

each of W and W’, equal to or different from each other, are selected from:

(i) Ci-C ₂₄ (hydro)(fluoro)carbon groups, possibly comprising one or more than one of H, O, and Cl; and

(ii) a group of any of formulas -CF3, -CF ₂ CI, -CF ₂ CF3, -CF(CF3)2 , -CF ₂ FI, -CFH ₂ , -CF ₂ CH ₃ , -CF ₂ CHF _2J -CF ₂ CH ₂ F, -CFZ*CH ₂ OH, -CFZ*COOH, -CFZ ^* COOR _h and -CFZ ^* -CH ₂ (OCH ₂ CH ₂ ) _k -OH, wherein k is ranging from 0 to 10, wherein Z ^* is F or CF3; R _h is a hydrocarbon chain.

[0028] According to an embodiment the anthracene moiety is not functionalized.

[0029] According to an embodiment, the monomer of the present invention is according to formula (V) or (VI):

wherein R _fa , T ^A and T ^B are as above-defined. [0030] Fluorinated (co)polymer

[0031] According to the present invention, R _fa and/or R¾ are fluorinated (co)polymers comprising recurring units derived from the polymerization of at least one ethylenically unsaturated fluorinated monomer.

[0032] According to another embodiment of the present invention, R _fa and/or R _¾ are fluorinated (co)polymers comprising recurring units derived from the polymerization of at least one ethylenically unsaturated fluorinated monomer, selected from the group consisting of:

C2-C8 (per)fluoroolefins, such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), pentafluoropropylene and hexafluoroisobutylene;

C2-C8 hydrogenated fluoroolefins, such as vinyl fluoride, 1 ,2-difluoroethylene, vinylidene fluoride (VDF) and trifluoroethylene;

- perfluoroalkylethylenes of formula CFh=CFI-R _h , wherein R _h is a C1-C6 perfluoroalkyl group;

- chloro- and/or bromo- and/or iodo-C2-C6 fluoroolefins such as chlorotrifluoroethylene (CTFE);

- (per)fluoroalkylvinylethers of formula (VII)

CF ₂ =CFO-R _g (VII)

wherein R _g is a C1-C6 (per)fluoroalkyl moiety, such as perfluoromethylvinylether (MVE);

- (per)fluoro-oxyalkylvinylethers of formula CF2=CFOXo, wherein Xo is a C1-C12 oxyalkyl group or a C1-C12 (per)fluorooxyalkyl group having one or more ether groups, e.g. perfluoro-2-propoxy-propyl group;

- fluoroalkyl-methoxy-vinylethers of formula CF ₂ =CF0CF ₂ 0Ri, wherein R, is a C1-C6 fluoro- or perfluoroalkyl group, e.g. -CF ₃ (MOVE3), -C2F ₅ , -C3F ₇ or a C1-C6 (per)fluorooxyalkyl group having one or more ether groups, e.g. -C2F ₅ -O-CF3;

- fluorodioxoles of formula (VIII):

wherein each of R _{ji ,} R _j2, R _j3 and R _j4 , equal to or different from each other, is independently a fluorine atom, a C1-C6 fluoro- or per(halo)fluoroalkyl group, optionally comprising one or more oxygen atoms, e.g. -CF3, -C ₂ F ₅ , -C3F7, -OCFs, -OCF2CF2OCF3.

[0033] According to another embodiment of the present invention, R _fa and/or R _¾ are fluorinated (co)polymers comprising recurring units derived from:

- C2-C8 (per)fluoroolefins, for example tetrafluoroethylene (TFE), hexafluoropropylene (FIFP), pentafluoropropylene or hexafluoroisobutylene; and

- (per)fluoroalkylvinylethers of formula (VII)

CF ₂ =CFO-R _g (VII)

wherein Rg is a C1-C6 (per)fluoroalkyl moiety, for example perfluoromethylvinylether (MVE).

[0034] According to another embodiment of the present invention, R _fa and/or R _¾ are fluorinated (co)polymers comprising recurring units derived from:

- from 50 to 99 mol.% of TFE, for example from 60 to 98 mol.% or from 64 to 97 mol.% of TFE, and

- from 1 to 50 mol.% of MVE, for example from 2 to 40 mol.% or from 3 to 36 mol.% of MVE.

[0035] According to an embodiment of the present invention, R _¾ is a fluorinated (co)polymer comprising at least one unit derived from a bis-olefin of formula (VIII):

wherein each of Ri, R ₂ , R3, R ₄ , Rs and R6, equal or different from each other, are H, F, C1-C5 alkyl or C1-C5 perfluoroalkyl, and

Z is a linear or branched C1-C18 alkylene or cycloalkylene radical, optionally containing oxygen atoms, preferably at least partially fluorinated, or a (per)fluoropolyoxyalkylene radical.

[0036] According to another embodiment of the present invention, R _¾ is a fluorinated (co)polymer comprising at least one unit derived from a bis- olefin of formula (IX):

wherein

each of R ₁ , R ₂ , R3, R ₄ , Rs and R6, equal or different from each other, are H, F, C1-C5 alkyl or C1-C5 perfluoroalkyl, and

j ranges between 2 and 10, preferably between 4 and 8.

[0037] According to a preferred embodiment of the present invention, R _¾ is a fluorinated (co)polymer comprising at least one unit derived from a bis- olefin of formula (IX) where R1, R2, R3, R4, Rs and R6 are H and j ranges between 5 and 7.

[0038] According to another preferred embodiment of the present invention, R _¾ is a fluorinated (co)polymer comprising:

a) recurring units derived from:

- from 50 to 99 mol.% of TFE, for example from 60 to 98 mol.% or from 64 to 97 mol.% of TFE, and

- from 1 to 50 mol.% of MVE, for example from 2 to 40 mol.% or from 3 to 36 mol.% of MVE;

b) units derived from a bis-olefin of formula (IX) where more preferably R1, R2, R3, R4, Rs and Re are FI and j ranges between 5 and 7.

[0039] According to an embodiment, the monomer of formula (la) or (lb) has a number average molecular weight Mn ranging from 1 ,000 to 130,000 g/mol, as determined by NMR.

[0040] Process for manufacturing the monomer of formula (la) and (lb) [0041] The present invention also relates to a process for manufacturing the monomer of the present invention, comprising the reaction of anthracene, possibly substituted with R _n , with the compound of formula (Xa) or (Xb):

X-CF ₂ -R _fa -T ^c (Xa)

X-CF ₂ -R _fb -T ^c (Xb) wherein

X is a halogen selected from the group consisting of I and Br;

R _fa is a fluorinated (co)polymer;

R _fb is a branched fluorinated (co)polymer, optionally comprising at least one group T ^c’ ;

T ^c and/or T ^c’ are selected from the group consisting of:

(i) Ci-C ₂₄ (hydro)(fluoro)carbon groups, possibly comprising one or more than one of H, O, and Cl; and

(ii) CF ₂ -X;

R is a halogen atom or an alkyl group, optionally branched, preferably an C1-C18 alkyl group optionally substituted with one or several halogen atoms; and

n is 0 or an integer from 1 to 9, preferably 0.

[0042] Preferably, X is I in formula (Xa) or (Xb) above.

[0043] Preferably T ^c and/or T ^c’ are selected from the group consisting of:

(i) a group of any of formulas -CF3, -CF ₂ CI, -CF ₂ CF3, -CF(CF3) _{2 ,} -CF ₂ FI, -CFH ₂ , -CF ₂ CH ₃ , -CF ₂ CHF _2J -CF ₂ CH ₂ F, -CFZ*CH ₂ OH, -CFZ*COOH, -CFZ ^* COOR _h and -CFZ ^* -CH ₂ (OCH ₂ CH ₂ ) _k -OH, wherein k is ranging from 0 to 10, wherein Z ^* is F or CF3; R _h is a hydrocarbon chain; and

(ii) CF ₂ -X.

[0044] According to an embodiment of the present invention, the reaction takes place in at least one fluorinated fluid.

[0045] According to an embodiment of the present invention, the reaction takes place at a temperature ranging from 180 to 300 °C, preferably from 200 to 250 °C.

[0046] According to certain embodiments, the compound of formula (Xa) or (Xb) can be preliminarily reacted with an activating compound/agent. The choice of the activating compound/agent is not limited, and typical organic chemistry strategies may be applied

[0047] Processes for preparing an adduct and adduct obtained therefrom

[0048] The present invention also relates to a process for manufacturing an adduct, comprising exposing the monomers of the present invention to UV light at a wavelength ranging from 280 nm to 600 nm, preferably from 300 nm to 450 nm.

[0049] The present invention also relates to an adduct obtained from this process.

[0050] The present invention also relates to an adduct obtained from exposing at least the monomer of the present invention to UV light at a wavelength ranging from 280 nm to 600 nm, preferably from 300 nm to 450 nm.

[0051] The monomers of the present invention can for example be used for the manufacture of films, coatings, or shaped articles. Films can be porous or non-porous and may have a thickness ranging from 0.05 to 500 pm. They can be flat films or may have a tubular shape. Coatings may be in the form of single layers or in the form of multiple layers having a higher thickness, typically ranging from 0.1 to 1000 pm and may fully or partially cover the underlying surface, which may have any shape and dimension. The coating can be formed prior to covering the surface and then applied to the surface or formed directly on the surface to be covered according to conventional methods, such as by casting a polymer or a composition on the surface and then by forming a film. Alternatively, a mixture of monomers can be casted on the surface to be coated and submitted to the conditions that allow the cycloaddition reaction to occur.

[0052] Non-limiting examples of surfaces to be coated are surfaces of polymer, metal, glass and ceramics articles, and paper or wood in the form of solid or porous fibers, woven sheets, non-woven sheets, or shaped articles.

[0053] Non limiting examples of shaped articles include solid or porous fibers, filaments, woven sheets, non-woven sheets, fuel line hoses, miniature circuit breakers (MCB), electrical switches and smart devices, surgical stents, surgical implants, medical devices and seals. Such articles can be manufactured according to conventional methods. In one embodiment, shaped articles can be manufactured by 3D printing techniques, including, but not limited to stereolithography (SLA), selective laser sintering (SLS) and fused filament fabrication (FFF). In one embodiment, the shaped composites can be manufactured by compression molding of a continuous fiber (glass, carbon) fabric using the usual processes to produce thermoset composites and thermoplastic composites, with the application of UV light when necessary.

[0054] The present invention also relates to a process for coating a surface, comprising:

a) applying to the surface the monomer of the present invention or the polymer blend of the present invention, and

b) exposing the surface to UV light at a wavelength ranging from 280 nm to 600 nm, preferably from 300 nm to 450 nm.

[0055] The present invention also relates to a process for manufacturing a shaped article, comprising:

a) applying to a mould the monomer of the present invention or the polymer blend of the present invention, and

b) exposing the surface to UV light at a wavelength ranging from 280 nm to 600 nm, preferably from 300 nm to 450 nm.

[0056] Processes for recycling an article comprising the adduct

[0057] The films (or membranes), coatings or shaped articles obtained from the monomers of the present invention can be recycled by exposure to UV light at a wavelength of less than 300 nm or by exposure to heat at a temperature of at least 180°C, preferably at least 195°C.

[0058] When films (or membranes), coatings or shaped articles obtained from the monomers of the present invention are recycled by exposure to heat, different means can be used. They can for example be recycled by using microwave energy or photo-irradiation to depolymerize the monomers.

[0059] The present invention also relates to a process for recycling a coating or a shaped article comprising the polymer adduct of the present invention, by exposing the coating or the shaped article to UV light at a wavelength of less than 300 nm.

[0060] The present invention also relates to a process for recycling a coating or a shaped article comprising the polymer adduct of the present invention, by heating the coating or the shaped article at a temperature higher 180°C, preferably higher 195°C, for example by using microwave energy of photo- irradiation.

[0061] Polymer blend

[0062] The present invention also relates to a polymer blend comprising at least 1 mol.% of the monomers according to the present invention, for example at least 2 mol.%, at least 5 mol.%, at least 10 mol.%, at least 20 mol.%, at least 30 mol.%, at least 40 mol.% or at least 50 mol.% of the polymer blend.

[0063] The polymer blends of the present invention may comprise others monomers as described below, for example monomers of formula (XI):

T ^D -CF ₂ -R _ha -T ^D’ (XI)

wherein

- R _ha is a fluorinated moiety selected from the group consisting of fluorinated polyether and fluorinated alkyl;

- T ^D and T ^D” , equal to or different from each other, are selected from the group consisting of:

(i) C1-C24 (hydro)(fluoro)carbon groups, possibly comprising one or more than one of H, O, and Cl; and

(ii) (hydro)(fluoro)carbon groups comprising at least an anthracene moiety (anthracene group) of formula (II):

wherein

- R is a halogen atom or an alkyl group, optionally branched, preferably an C1 C18 alkyl group optionally substituted with one or several halogen atoms; and

- n is 0 or an integer from 1 to 9, preferably 0;

with the proviso that at least one of T ^D and T ^D’ comprises an anthracene moiety according to formula (II).

[0064] In some embodiments, the polymer blend of the present invention comprises at least 1 mol.% of the monomers of formula (XI), for example at least 2 mol.%, at least 5 mol.%, at least 10 mol.%, at least 20 mol.%, at least 30 mol.%, at least 40 mol.% or at least 50 mol.% of the polymer blend.

[0065] Fluorinated po!yether

[0066] According to the present invention, the polymer blend may comprise at least an additional monomer of formula (XI) in which R _ha may be fluorinated polyethers. These polyethers may comprise at least one fluoropolyether (PFPE) chain.

According to an embodiment of the present invention, the polymer blend comprises at least an additional monomer of formula (XI), in which R _ha is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (XII):

(CFXi) _a O(Rh)(CFX ₂ )b (XII)

wherein

- a and b, independently form each other, are integer equal to at least 1 ;

- Xi and X ₂ , independently form each other, are F or CF ₃ , provided that when a and/or b are higher than 1 , X ₁ and X ₂ are F;

- (R _h ) comprises repeating units being independently selected from the group consisting of:

(i) -CFX ₁ O-, wherein X ₁ is F or CF3;

(ii) -CFX ₁ CFX ₁ O-, wherein X ₁ , equal or different at each occurrence, is F or CF3, with the proviso that at least one of X ₁ is F;

(iii) -CF ₂ CF ₂ CW ₂ 0-, wherein each W is independently from each other, F, Cl or H;

(iv) -CF ₂ CF ₂ CF ₂ CF ₂ 0-;

(v) -(CF ₂ ) _j -CFZ-0- wherein j is an integer from 0 to 3 and Z is a group of general formula -O-Ri-T, wherein R, is a fluoropolyoxyalkene chain comprising 0 to 10 recurring units selected from the group consisting of CFX ₁ O , CF ₂ CFX _I O, CF ₂ CF ₂ CF ₂ 0, CF ₂ CF ₂ CF ₂ CF ₂ 0, wherein each X ₁ is independently from each other F or CF3 and T is a C ₁ -C3 perfluoroalkyl group.

[0067] More preferably, a and b, independently form each other, are integer 1 to 10, even more preferably from 1 to 3. [0068] According to an embodiment of the present invention, the polymer blend comprises at least an additional monomer of formula (XI) in which R _ha is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (XIII):

-[(CFX ¹ 0)gi(CFX ² CFX ³ 0)g ₂ (CF ₂ CF ₂ CF ₂ 0)g3(CF ₂ CF ₂ CF ₂ CF ₂ 0)g ₄ ]- (XIII) wherein

X ¹ is, independently at each occurrence, F or CF3,

- X ² and X ³ , independently from each other and at each occurrence, are F or CF3, with the proviso that at least one of X is F;

- g1 , g2 , g3, and g4, independently from each other, are integers >0, such that the sum (g1 +g2+g3+g4) is from 2 to 300, preferably from 2 to 100; should at least two of g1 , g2, g3 and g4 be different from zero, the different recurring units are generally statistically distributed along the chain.

[0069] According to another embodiment of the present invention, the polymer blend comprises at least an additional monomer of formula (XI) in which Rha is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (XIV):

[ (CF ₂ 0) _n (CF ₂ CF ₂ 0) _m ] _p (XIV)

wherein

- n and m, independently from each other, are integers ³0, such that the number average molecular weight (Mn) is between 400 and 10,000, preferably between 1 ,000 and 8,000; both m and n are preferably different from zero, with the ratio m/m being preferably comprised between 0.1 and 10, for example 0.5 and 10.

[0070] According to another embodiment of the present invention, the polymer blend comprises at least an additional monomer of formula (XI) in which Rha is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (XV):

-[(CF ₂ CF ₂ 0) _bi (CF ₂ 0)b2(CF(CF3)0)b3(CF2CF(CF ₃ )0)b4]- (XV) wherein

- b1 , b2, b3, b4, independently from each other, are integers ³0, such that the number average molecular weight (Mn) is between 400 and 10,000, preferably between 1 ,000 and 8,000; preferably b1 is 0, and b2, b3, b4 are > 0, with the ratio b4/(b2+b3) being >1.

[0071] According to another embodiment of the present invention, the polymer blend comprises at least an additional monomer of formula (XI) in which Rha is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (XVI):

-[(CF2CF20)CI (CF20)C2(CF2(CF2)CWCF ₂ 0)C3]- (XVI) wherein

- cw is 1 or 2;

- d , c2, and c3 independently from each other, are integers ³0, such that the number average molecular weight (Mn) is between 400 and 10,000, preferably between 1 ,000 and 8,000; preferably d , c2 and c3 are all > 0, with the ratio c3/(d +c2) being generally lower than 0.2.

[0072] According to another embodiment of the present invention, the polymer blend comprises at least an additional monomer of formula (XI) in which Rha is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (XVII):

-[(CF ₂ CF(CF ₃ )0) _d ]- (XVII)

wherein

- d is an integer > 0 such that the number average molecular weight (Mn) is between 400 and 10,000, preferably between 1 ,000 and 8,000.

[0073] According to another embodiment of the present invention, the polymer blend comprises at least an additional monomer of formula (XI) in which Rha is a fluorinated polyether is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (XIII):

-[(CF2CF2C(Hal ^* )20)ei-(CF2CF2CH20)e2-(CF2CF ₂ CH(Hal ^* )0)e3]- (XVIII) wherein

- Hal ^* , equal or different at each occurrence, is a halogen selected from fluorine and chlorine atoms, preferably a fluorine atom;

- e1 , e2, and e3, independently from each other, are integers ³0, such that the sum (e1 +e2+e3) sum is from 2 and 300.

[0074] According to an embodiment, the chain Rf _a ay be selected so as to possess a number average molecular weight (Mn) ranging from 400 to 10,000 g/mol, preferably of 750 to 10,000 g/mol, even more preferably of 1 ,000 to 8,000 g/mol, as determined by NMR.

[0075] Fluorinated alkyl monomers

[0076] As used herein, the term“fluorinated alkyl” refers to a linear, branched or cyclic hydrocarbon chain in which some or all of the hydrogen atoms are replaced by fluorine atoms.

[0077] The term “fluorinated alkyl” may include fluorinated alkyl or fluorinated heteroalkyl that are optionally substituted by halogen or hydroxyl groups or that are optionally unsaturated.

[0078] According to an embodiment of the present invention, the polymer blend comprises at least an additional monomer of formula (XI) in which R _ha is a fluorinated alkyl and for example comprise from 1 to 20 carbon atoms, from 2 to 15 carbon atoms or from 3 to 10 carbon atoms.

[0079] According to another embodiment, the polymer blend comprises at least an additional monomer of formula (XI) in which R _ha is (CF2) _x wherein x is from 0 to 20.

[0080] In a preferred embodiment, the polymer blend comprises at least an additional monomer of formula (XI) in which R _ha is a C ₄ -Cio fluorinated alkyl. Examples of preferred C ₄ -Cio fluorinated alkyl according to the invention are -C(CF3)2-, -C ₄ Fs- or -C2F ₄ -

[0081] According to an embodiment, the monomer of formula (XI) has a number average molecular weight Mn ranging from 200 to 1 ,000 g/mol, as determined by NMR.

[0082] The polymer blends of the present invention may also comprise additives, for example selected from the group consisting of chopped and continuous glass fibers, chopped and continuous carbon fibers, lubricants, plasticizers, fire retardants, stabilizers and pigments.

[0083] The polymer blends of the present invention may also comprise at least one solvent or a mixture of solvents selected from the group consisting of:

- fluorinated solvents such as (per)fluoroethers, (per)fluoropolyethers, (per)fluoralkanes, (per)fluoroamines, (per)fluoroamides,

(per)fluorolactams; fluoroaromatics solvents such as hexafluorobenzene and hexafluoroxylene); and

- hydrogenated solvents such as THF and toluene, THF being preferred.

[0084] Polymer blends may be manufactured according to mixing/blending methods known in the art.

[0085] Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

[0086] EXAMPLES

[0087] The invention will be now described in more detail with reference to the following examples, whose purpose is merely illustrative and not intended to limit the scope of the invention.

Provided below several examples of synthesis of monomers according to the invention by a radical mechanism wherein the monomers are as follows:

- in example 1 , FP#1 is a CF ₂ I-TFE-MVE-CF ₂ I (“copolymer MVE/TFE”), a copolymer with an average 85/15 TFE/MVE molar composition and -CF ₂ I iodinated end groups,

- in example 4, FP#2 is a branched MVE/TFE copolymer (MVE/TVE/CH ₂ =CH-(CF ₂ )-CH=CH ₂ ), a copolymer with an average 65/35 TFE/MVE molar composition and -CF ₂ I iodinated end groups.

[0088] Starting Materials

Anthracene from Sigma Aldrich

FP#1 : CF ₂ I-TFE-MVE-CF ₂ I, a copolymer with an average 85/15 TFE/MVE molar composition and -CF ₂ I iodinated end groups, obtained by a process as described in patent documents US 4,243,770 and EP 683149, incorporated herein by reference

FP#2: Branched MVE/TFE copolymer (MVE/TVE/CH ₂ =CH-(CF ₂ )- CFI=CFI ₂ ), obtained by a process as described in patent application WO 2012/168351 and patents US 5,585,449, US 5,902,857, US 5,948,868 incorporated herein by reference Solvents: Galden ^® PFPE HT-270, HT-110, HT-230, HT-55 commercially available from Solvay Specialty Polymers Italy, and Fluorinert FC72 commercially available from 3M

[0089] Methods

[090] ¹ H-NMR analyses were performed on a Varian Mercury 300 MFIz spectrometer using tetramethylsilane (TMS) as internal standard.

[091] ¹⁹ F-NMR analyses were performed on a Varian Mercury 300 MHz spectrometer using CFC as internal standard.

[0092] UV absorption in solvent (CeFe), using a UV lamp 200 Perkin-Elmer element 3 with 1 cm length

[0093] DSC was used to determine the glass transition temperature (Tg). DSC experiments were carried out using a TA Instrument Q100. DSC curves were recorded by heating, cooling, re-heating, and then re-cooling the sample between 25°C and 400C at a heating and cooling rate of 10°

C/min. All DSC measurements were taken under a nitrogen purge. The reported Tg is provided using the second heat curve unless otherwise noted.

[0094] Tensile properties of the membranes are determined using DIN638 and Type V bars.

[0095] Example 1 - Synthesis of an anthracene functionalized 9,9’-MVE/TFE copolymer (Anthr-FP#1 )

(represented here Anthr ₂ -FP#1 )

[0096] Anthracene (0,298 g, 1 ,673 mmol), FP#1 (CF ₂ I-TVE-MVE-CF ₂ I - EW = 4303 g/eq; 1 ,394 meq; 0,697 mmol) and Galden ^® Fluid FIT-270 (40 ml) are all placed in a glass round bottom flask equipped with an internal thermometer, a gas inlet and a reflux condenser. The cooling liquid is Galden ^® Fluid HT-1 10 and it is cooled to 15°C. Stirring is maintained at 800 rpm while the mixture is heated to 80°C and it is degassed with N ₂ (3 N ^* L/hr) for 20 min from the gas inlet. Once degassing is finished, N ₂ flux is stopped and the reaction temperature is raised to 220°C with vigorous stirring at 800 rpm. Heating and stirring were maintained for a total of 6 hours. The crude reaction mixture was then cooled to room temperature and the solvent HT-270 was decanted. A dark tan waxy solid remained in the round bottomed flask, was placed in an Erlenmeyer flask and stirred vigorously with Galden ^® fluid HT-55 (30 ml) at 20°C. During stirring, the waxy solid breaks up forming a solid suspension in HT-55. The suspension was then centrifuged at 4000 rpm for 20 min at 20°C. The pellets obtained were washed several times in HT-55 (30 ml), then the waxy solid was suspended in 30 ml Na ₂ S ₂ 03aq (30 ml) and stirred at 20°C for 20 min order to reduce and extract any residual l ₂ or HI from the solid. Finally, the waxy solid was suspended and stirred at 20°C for 20 min in THF (30 ml) in order to extract H ₂ 0 from the solid. The solid was then dried in a vacuum oven at 60°C with 0,1 mbar PRES for 4 hrs. The HT-55 washings were evaporated.

[0097] Results:

Reaction selectivity towards desired Anthr ₂ -FP#1 = 61 mol.%

Isolated Yield of Anthr ₂ -FP#1 = 58 % with purity > 98 mol.%

Loss of Anthr ₂ -FP#1 = 5 % (in HT-55 washings).

Solubility (C6F6 at 20°C): 10% w/v.

Mw = 8,900 g/mol

372 = 5520 IVMcrrr ¹

NMR:

¹⁹ F-NMR (C6F6 as solvent): ppm -54 (CF3O of MVE; s); ppm -114, -118, -120 (CF ₂ of TFE; m); ppm -136 (CF of MVE; s)

¹ H-NMR (C6F6 as solvent; TMS): ppm 9, 8.8, 8.6, 8 (H-Aromatics, including meso-ring)

[0098] Example 2 - Synthesis of a membrane with Anthr-FP#1

[0099] A 10 w/w% homogeneous solution of the anthracene-functionalized 9,9’- copolymer MVE/TFE in CeF6 (200 mg of Anthr-FP#1 in 2 g CeF6 prepared according to example 1) is evaporated in a vacuum oven (60°C, 800 mbar PRES for 60 min followed by 60 min at 100°C and 800 mbar PRES). The solution is contained in a 5.5 cm diameter Petri dish yielding a dry, transparent membrane (or film) with an average thickness of 46 pm and a dry concentration of 0,228M.

[00100] The dry membrane in the Petri dish in then placed in a ItalQuartz UV apparatus equipped with a lamp chamber, an irradiation plate with centering cross-hairs, a glass plate filter in order to cut wavelengths <300 nm and an inlet for N2 insuflation to inertize the environment. P = 800 W was chosen for this Example.

[00101] The sample was then irradiated for a total of 27 min, allowing for periodic cooling in order not to exceed 80-84°C, measuring the conversion at regular time intervals. The conversion was measured by stopping the UV irradiation and taking a ca. 4 mg sample of the membrane, placing it in a quartz cuvette and dissolving it in ca. 3 ml of C6F6. Direct comparison of the UV Absorbance at l = 373 nm (A373) with A373 at t=0 gave the conversion at that time interval as well as the composition in terms of dimers, trimers and higher order oligomers.

[00102] After 27 min of UV irradiation, n ^meso = 85.8 mol% corresponding to heptamers as the major oligomeric species detected in the UV cuvette. See Table 1 below.

Table 1

[00103] Example 3 - Recyclability of a membrane by heat

[00104] A membrane was prepared and photo-oligomerized as described in Example 2 and up to a n ^meso = 67.1 mol%.

[00105] The membrane was then placed in a Buchi oven in an inert (N2) atmosphere and heated at 195°C for a total of 18 min; 230°C for a total of 18 min and 260°C for a total of 9 min. This experiment was performed in the presence of light.

[00106] After 45 minutes of heating, r| ^meso = Q.48 mol.%. See Table 2 below.

Table 2

[00107] Example 4 - Tensile properties of a membrane made of Anthr-FP#1 [00108] A membrane was prepared and photo-oligomerized as described in Example 2 and up to a h meso ^— 67.1 mol%.

[00109] DSC: Tg = 24,9°C

[001 10] Tensile properties (@80°C) (DIN638 TypeV)

Thickness (mm) = 0.23 ± 0.04

Stress at break (MPa) = 1.1 ± 0.1

Strain at break (%) = 206 ± 37

[001 1 1] Example 5 - Recyclability of a membrane by UV

[001 12] A membrane was obtained from Anthr-FP#1 as described in Example 2, up to h meso (%) = 61.6 %.

[001 13] The membrane was placed in a glass Petri dish of 3.5 cm diameter and centered upon the heated thermal plate of a Wood Light UV instrument with 6 independent UV light sources. While priming the Wood Light instrument, the irradiation chamber was purged with N ₂ at a rate of approximately 5 NL/h. The sample was exposed to UV light (254nm, 30 W).

[001 14] After 120 minutes of UV, r| ^meso = 9.27 mol.%. See Table 3 below.

Table 3

[001 15] Example 6 - Polymerization-depolymerization cycles

[001 16] A membrane was obtained from Anthr-FP#1 as described in Example 2 up to Hmeso (%) = 65.5 %. The membrane was then depolymerized according to the procedure described in example 5 down to h meso (%) = 7%.

[001 17] This cycle was repeated up to H _meso (%) = 51.7 % and then down to H _meso (%) = 14%. See Table 4 below.

Table 4

[00118] Example 7 - Recyclability of a membrane by microwave energy

[00119] A membrane was obtained from Anthr-FP#1 as described in Example 2 up to H _meso (%) = 84.5 %, was treated in a microwave oven (LG-Gr microwave oven) with 360W and 600W power, purged with with 4 Nl/h of nitrogen for 30minutes before starting the reaction. Table 5 below reports the decrease of Mw of the micro-wave treated sample at different irradiation times down to Hmeso (%) = 6.6 %. The obtained sample was then polymerized again according to Example 2 up to H _meso (%) = 68.1 % and depolymerized with micro-wave assisted protocol down to to h meso (%) = 1.2 %.

28 SSPI 2018/004

Table 5

[00120] Example 8 - Synthesis of a polyfunctional anthracene functionalized branched MVE/TFE copolymer (Anthr-FP#2)

[00121] FP#2 (branched MVE/TFE copolymer - 5,00 g; Mn = 106,000 g/mole, EW = 26,500 g/eq, 188.7 meq of -CF2l) was placed in a glass round-bottomed flask equipped with an internal thermometer, a condensation column cooled to 10°C with Galden® HT-1 10 refrigerant, a gas (N2) inlet valve, a liquid dripping funnel and a solid micro-dispenser. The equipment was then degassed with N2 fluxed at a rate of 4 NL/h during which time Galden® HT-270 (solvent, 150 ml) was added employing the liquid dripping funnel with vigorous (800 rpm) stirring by means of a magnetic stirring bar. The resulting emulsion is warmed to 100°C and degassing of the emulsion continued for a total of 40 min. Anthracene (30 mg, 168.5 pmoles) was added employing the solid micro-dispenser and the emulsion was heated to 170°C. The stirring is increased to 1000 rpm and the reaction T is raised to 230°C and kept at 235°C for a total of 5.5 hrs.

[00122] At the end of the reaction time, the crude mixture is cooled and poured in a FEP centrifuge vessel and centrifuged at 20°C, 4000 rpm for 40 min. Analysis of the supernatant phase demonstrated that HT-270 was the only component and was is discarded. The solid, waxy material was dispersed in Galden® PFPE HT-55 (50 ml) at 20°C. The Galden® PFPE HT-55 suspension was then centrifuged at 4000 rpm, at 20°C for 40 min. The pale-orange waxy material was then re-centrifuged in a fresh aliquot (50 ml) of galden HT-55. This washing/centrifuge operation was repeated a total of 3 times always keeping the supernatant (Galden® PFPE HT-55). The supernatants were pooled together and distilled at 60°C and at a reduced P (100 mbar). Following the distillation, a pale yellow, viscous oil was obtained. The pale yellow, viscous oil and the pale orange waxy pellet were kept separate and analysed.

[00123] Total Yield (oil+wax) = 97 mol.%

[00124] Analysis of the pale yellow, viscous oil

Anthr _2,92 -FP#2

Selectivity Anthr _2,92 -FP#2 = 75 mol.%

e369 = 5,955 IVMcnrr ¹ = 2,132 Eq- ¹ cnrr ^{1 1} H-NMR (CF3CH2OH): d = 8.3 (m), 8,2 (s), 8.175 (d), 7.95 (m), 7.6 (d.m).

¹⁹ F-NMR (CF3CH2OH): d = -56.8 (CF ₃ 0-; MVE); -120; -120.5; -122.4; -123.5 (-CF2-; TFE)

[00125] Analysis of the purified waxy, pale orange pellet

Anthr _{3 6} -FP#2

Selectivity Anthr3 _, 6-FP#2 = 25 mol.%

£369 = 8,238 IVMcrrr ¹ = 2,132 Eq- ¹ crrr ¹

¹ H-NMR (std. CF3CH ₂ OH): d = 8.3 (m), 8.2 (s), 8.175 (d), 7.95 (m), 7.6 (d,m)

¹⁹ F-NMR (std. CF3CH ₂ OH): d = -56.8 (CF ₃ 0-; MVE); -120; -120.5; -

122.4; -123.5 (-CF2-; TFE)

[00126] Example 9 - Crosslinking of Anthr-FP#2

[00127] Anthr _{2 92} -FP#2 cross-linked membrane and Anthr3 _.6 -FP 2 cross-linked membrane were obtained as described in Example 2 using FC72 as solvent. See respectively Tables 6 and 7 below.

Table 6

Table 7

[00128] Characterization of membrane Anthr2 ₉₂ -FP#2

[00129] DSC: Tg = -37.5°C

[00130] Tensile properties (@23°C) (DIN638 TypeV)

Thickness (mm) = 0.31 ± 0.08

Stress at break (MPa) = 1.0 ± 0.0

Strain at break (%)= 303 ± 5

[00131] Characterization of membrane Anthr3 ₆ -FP#2

[00132] DSC: Tg = -7.6°C

[00133] Example 10 - Recyclability of membranes of Example 8 by heat

[00134] A 300 pm thick membrane obtained from cross-linking of polyfunctional Anthr _2.92 -FP#2 as described in Example 9, up to Mw = 584,060 g/mol was put on a petri dish in an oven. The oven chamber was inertized by 3 cycles of vacuum/N2. The final atmosphere was N2 at 0,95 atm. Temperature was increased to obtain thermal de-crosslinking down to a final Mw = 129,320 g/mol. See Table 8 below.

Table 8

[00135] A 264 mhh thick membrane obtained from cross-linking of polyfunctional Anthr3 _.6 -FP#2 as described in Example 9, up to a Mw > 900,000 was de- crosslinked following the same procedure described above, down to Mw = 111 ,636 g/mol. See Table 9 below.

Table 9