WO2019162493A1

WO2019162493A1 - Fluorinated monomers comprising anthracene moieties

Info

Publication number: WO2019162493A1
Application number: PCT/EP2019/054562
Authority: WO
Inventors: Ivan Diego WLASSICS; Stefano Millefanti; John Scott Flanagan; Joel POLLINO; Kermit S. Kwan; Davide Vicino
Original assignee: Solvay Specialty Polymers Italy S.P.A.
Priority date: 2018-02-23
Filing date: 2019-02-25
Publication date: 2019-08-29
Also published as: WO2019162491A1

Abstract

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 adducts obtained from the fluorinated monomers, as well as to the process for preparing the adducts.

Description

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 (I):

T^A-CF₂-R_fa-T^A’ (I)

wherein

- R_fa is a fluorinated polyether;

- 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 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 280 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 (I):

T^A-CF₂-R_fa-T^A’ (I)

wherein

- R_fa is a fluorinated polyether;

- 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

wherein

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

with the proviso that at least one of 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, R_fa is a fluorinated polyether. R_fa is preferably a linear fluorinated polyether. Monomers according to formula (I) 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). Monomers according to formula (I) presents an anthracene functionality of 1 when one of T^A or T^A’ consist in a (hydro)(fluoro)carbon group comprising at least an anthracene moiety (anthracene group) of formula (II). Very often the functionality of reaction product will range between 1 and 2, and the functionality of the reaction products depends on the starting materials.

[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-CF₂-R_fa-T^A’ (I)

wherein

- R_fa is a fluorinated polyether;

- 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

wherein

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

with the proviso that at least one of 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 (III):

T^B-CF₂-R_fa-T^B’ (III)

wherein

- R_fa is a fluorinated polyether;

- 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, -CF₂CI, -CF₂CF3, -CF(CF3)_{2 ,} -CF₂FI, -

CFH₂, -CF2CH3, -CF2CHF2, -CF2CH2F, -CFZ*CH₂OH, - CFZ*COOH, -CFZ*COORi and -CFZ*-CH₂(OCH₂CH₂)_k-OH, wherein k is ranging from 0 to 10, wherein Z^* is F or CF3; Ri is a C₁-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 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 50,000 g/mol, preferably from 800 to 40,000 g/mol, even more preferably from 1 ,000 to 30,000 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 chain), possibly comprising variable fractions of monomers wherein two (because of the linear 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, the monomers may for example consist of a major amount of monomers of formula (I) [T^A-CF2-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 (I) [T^A-CF2-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). Alternatively, the monomers may consist of a minor amount of monomers of formula (I) [T^A-CF₂-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 major amount of monomers of formula (I) [T^A-CF₂-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 1.0, preferably greater than 1.05, more preferably greater than 1.1.

[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 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.

[0024] The side products may be of formula (IV):

W-CF₂-R_fa-W’ (IV)

wherein:

R_fa is a chain R_fa, as above detailed; each of W and W’, equal to or different from each other, are selected from:

(ii) a group of any of formulas -CF3, -CF2CI, -CF2CF3, -CF(CF3)2 , -CF2FI, -CFH₂, -CF₂CH3, -CF₂CHF₂, -CF₂CH₂F, -CFZ*CH₂OH, -CFZ*COOH,

-CFZ*COOR_h and -CFZ*-CH₂(OCH₂CH₂)_k-OH, wherein k is ranging from 0 to 10, wherein Z* is F or CF₃; R_h is a hydrocarbon chain.

[0025] According to an embodiment the anthracene moiety is not functionalized.

[0026] 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.

[0027] Fluorinated po!yether

[0028] According to the present invention, R_fa is a fluorinated polyether.

[0029] According to an embodiment of the present invention, R_fa is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain.

[0030] According to an embodiment of the present invention, R_fa is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (VII):

(CFXi)_a O(Rh)(CFX₂)b (VII)

wherein

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

- Xi and X2, independently form each other, are F or CF3, provided that when a and/or b are higher than 1 , X1 and X2 are F;

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

(i) -CFX₁O-, wherein X₁ is F or CF3;

(ii) -CFX₁CFX₁O-, wherein X₁ , equal or different at each occurrence, is F or CF3, with the proviso that at least one of X₁ is F; (iii) -CF2CF2CW2O-, wherein each W is independently from each other, F, Cl or H;

(iv) -CF2CF2CF2CF2O-;

(v) -(CF₂)_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 CFX1O , CF2CFX1O, CF2CF2CF2O, CF2CF2CF2CF2O, wherein each X1 is independently from each other F or CF3 and T is a C1-C3 perfluoroalkyl group.

[0031] More preferably, a and b, independently form each other, are integer 1 to 10, even more preferably from 1 to 3.

[0032] According to an embodiment of the present invention, R_fa is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (VIII):

-[(CFX¹0)gi(CFX²CFX³0)g₂(CF₂CF₂CF₂0)g3(CF₂CF₂CF₂CF₂0)g₄]- (VIII) wherein

X¹ is, independently at each occurence, F or CF3,

- X² and X³, independently from each other and at each occurence, 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.

[0033] According to another embodiment of the present invention, R_fa is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (IX):

[ (CF₂0)_n (CF₂CF₂0)_m ]_p (IX)

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 1000 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. [0034] According to another embodiment of the present invention, R_fa is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (X):

-[(CF₂CF₂0)bi (CF₂0)_b2(CF(CF3)0)b3(CF₂CF(CF₃)0)b4]- (X) 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 400 and 8,000; preferably b1 is 0, and b2, b3, b4 are > 0, with the ratio b4/(b2+b3) being >1.

[0035] According to another embodiment of the present invention, R_fa is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (XI):

-[(CF₂CF₂0)ci(CF₂0)c2(CF₂(CF₂)cwCF₂0)c3]- (XI)

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.

[0036] According to another embodiment of the present invention, R_fa is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (XII):

-[(CF₂CF(CF₃)0)_d]- (XII)

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.

[0037] According to another embodiment of the present invention, R_fa is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (XIII):

-[(CF₂CF₂C(Hal^*)₂0)ei-(CF₂CF₂CH₂0)e2-(CF₂CF₂CH(Hal^*)0)e3]- (XIII) 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.

[0038] According to an embodiment, the chain Rf_a may 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.

[0039] Process for manufacturing the monomer of formula (I)

[0040] 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 (XIV):

X-CF₂-R_fa-T^c (XIV)

wherein

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

Rfa is a fluorinated (co)polymer;

T^c is selected from the group consisting of:

(ii) CF2-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.

[0041] Preferably, X is I in formula (XIV) above.

[0042] Preferably T^c is selected from the group consisting of:

(i) a group of any of formulas -CF3, -CF₂CI, -CF₂CF3, -CF(CF3)_{2 ,} -CF₂FI, -CFH₂, -CF₂CH3, -CF₂CHF₂, -CF₂CH₂F, -CFZ*CH₂OH, -CFZ*COOH, -CFZ*COOR_h and -CFZ*-CH₂(OCH₂CH₂)_k-OH, wherein k is ranging from 0 to 10, wherein Z^* is F or CF3; R_h is a hydrocarbon chain; and

(ii) CF₂-X.

[0043] According to an embodiment of the present invention, the reaction takes place in at least one fluorinated fluid. [0044] According to an embodiment of the present invention, the reaction takes place at a temperature ranging from 150 to 300 °C, preferably from 180 to 220 °C.

[0045] According to certain embodiments, the compound of formula (XIV) 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

[0046] Processes for preparing an adduct and adduct obtained therefrom

[0047] 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.

[0048] The present invention also relates to an adduct obtained from this process.

[0049] 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.

[0050] 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.

[0051] 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. [0052] 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.

[0053] 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.

[0054] 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

[0055] Processes for recycling an article comprising the adduct

[0056] 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.

[0057] 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. [0058] 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.

[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 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.

[0060] Polymer blend

[0061] 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.

[0062] 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.

[0063] 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, and THF is preferred.

[0064] Polymer blends may be manufactured according to mixing/blending methods known in the art.

[0065] 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. [0066] EXAMPLES

[0067] 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.

[0068] Starting Materials

Anthracene from Sigma Aldrich

PTFE: a,w-diiodo-PFPE obtained as described in US 2002/0169276

Solvents: Galden^® PFPE HT-270, HT-110, HT-230, HT-55 commercially available from Solvay Specialty Polymers Italy

[0069] Methods

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

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

[0072] UV absorption in solvent (CeFe), using a UV lamp 200 Perkin-Elmer element 3 with 1 cm length

[0073] 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 400°C 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.

[0074] Example 1 - Synthesis of 9,9’-PFPE anthracene (Anthr-PFPE)

[0075] a,w-diiodo-PFPE (4,00 g; 12,81 meq -OCF2I) was placed in a glass round-bottomed flask equipped with an internal thermometer, a condensation column cooled to 10°C with Galden® PFPE HT-110 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 2 NL/h during which time Galden® PFPE HT-230 (solvent, 35 ml) was added employing the liquid dripping funnel with vigorous (800 rpm) stirring by means of a magnetic stirring bar. The resulting homogeneous solution is warmed to 100°C and degassing of the solution continued for a total of 40 min. Anthracene (3,00 g, 16,85 mmoles) was added employing the solid micro-dispenser and the heterogeneous solution was heated to 200°C by means of an oil bath. N2 flux is stopped and the reaction mixture is kept under static inert atmosphere by means of a latex balloon filled with N2. The stirring is increased to 1000 rpm and the reaction T is kept at 200°C for a total of 8 hrs. Purple fumes evolve during this stage indicating the homolitic cleavage of the -CF2-I bond, and formation of the desired - CF2-Anthracene bond with concomitant formation of HI, following re- aromatization of Anthracene’s meso ring.

[0076] At the end of the reaction time, the crude mixture is cooled and filtered upon a PTFE 0.45 pm membrane. The filtered, pale pink solution is kept aside and the solid filtrate is added to the residues in the reaction vessel. The unified solid residues are then stirred in 30 ml of Galden HT-55 fluid at 800 rpm, 40°C and for 15 min. The heterogeneous solution is filtered upon a PTFE 0,45 pm membrane and the filtered solution is added to the first filtrate. The solid is washed with 30 ml of CF3O-CFCI-CF2CI at 40°C, 800 rpm for 15 min. All filtrated are pooled and treated with a catalytic amount of Na₂S₂03^*5H₂0(s) to reduce free I2. The reduced organic solution is filtered upon PTFE 0,45 pm and then distilled at 150°C, 1 atm to remove all low-boiling organics, followed by a 10 min distillation at 200°C and 0,1 mbar to remove the trace amounts of resudual high-boiling organics (Galden® PFPE HT-230) and sublime residual, unreacted Anthracene. A dark yellow, viscous oil is obtained.

[0077] Analysis of the yellow, viscous oil

Anthn_.e-PFPE - f =1 ,60 (NMR)

[0078] Results:

Yield = 85.7 mol%

Selectivity towards -OCF2-Anthr = 99.8 mol%

Conversion -OCF2-I = 91.5 mol%

£363 = 2,619 IVMcrrr¹; 1 ,552 Eq-¹cm-¹ (C6F6 at l_MAc= 363nm)

Mw = 3,399 g/mol PE = 2, 169 g/eq

72 % Anthr₂-PFPE =Anthr-CF₂-PFPE-OCF₂-Anthr)

25,5% Anthr1 -PFPE =Antr-CF₂-PFPE-OCF₂(H/l/COOH)

2,3 % PFPE = (H/l/COOH)-CF₂-PFPE-OCF₂(COOH/l/H)

DSC: Tg = -105°C

[0079] Example 2 - Photo-oligomerization of Anthr-PFPE of Example 1

[0080] A 10 w/w% homogeneous solution of the anthracene-functionalized PFPE in C6F6 (200mg of Anthr-PFPE1 in 2 g C6F6 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 product is placed in a 3 cm diameter Petri dish yielding a solvent-free, transparent oil with an average thickness of 100 pm and a dry concentration of 0,747M.

[0081] 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.

[0082] The sample was then irradiated as described in Table 1 below.

Table 1

[0083] Example 3 - Recyclability Anthr-PFPE oligomer of Example 2 by microwave [0084] A material obtained as described in Example 2 from photo-oligomerization of the 9,9’-PFPE-Anthracene up to n^meso = 36.1 % was de-oligomerized 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 2 below reports the decrease of Mw of the micro-wave treated sample at different irradiation times down to h meso (%) = 0.6 %.

Table 2

[0085] Example 4 - Cycle of recyclability of an oligomer obtained from Anthr- PFPE

[0086] The material obtained after de-oligomerization in Example 3 (Mw=3,440), was oligomerized using UV and the same equipment described in Example 2, up to q_meso = 44.5% and then de-oligomerized again using microwave to h meso^— 2,3 %. See Table 3 below.

Table 3

[0087] Example 5 - Recyclability of the Anthr-PFPE oligomer of Example 2 by UV [0088] A material obtained as described in Example 2 from photo-oligomerization of the 9,9’-PFPE-Anthracene up to n^meso = 37.7 % was de-oligomerized 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 N₂ at a rate of approximately 5 NL/h. The sample was exposed to UV light (254nm, 30W). Table 4 below reports the decrease of Mw of the UV treated sample at different irradiation times down to h meso (%) = 1.8 %.

Table 4

[0089] Example 6 - Recyclability of the Anthr-PFPE oligomer of Example 2 by heat

[0090] A material obtained as described in Example 2 from photo-oligomerization of the 9,9’-PFPE-Anthracene up to n^meso = 37.4 % was placed in a Buchi oven in an inert (N₂) atmosphere and heated at sevreal temperatures described in Table 5 for a total of 45 min. This experiment was performed in the presence of light.

[0091] After 45 minutes of heating, r|^meso = 3 2 mol.%. See Table 5 below.

Table 5

Claims

Claim 1. A monomer of formula (I):

T^A-CF₂-R_fa-T^A’ (la)

wherein

- R_fa is a fluorinated polyether;

wherein

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

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

Claim 2. The monomer of claim 1 , having a number average molecular weight Mn ranging from 400 to 5,000 g/mol, as determined by NMR.

Claim 3. The monomer of claim 1 or 2, of formula (III):

T^B-CF₂-R_fa-T^B’ (III)

wherein

- R_fa is a fluorinated polyether;

(i) a group of any of formulas -CF3, -CF₂CI, -CF₂CF3, -CF(CF3)_{2 ,} -CF₂FI, -CFFI₂, -CF₂CH₃, -CF₂CHF_2J -CF₂CH₂F, -CFZ^*CH₂OH, -CFZ^*COOH, -CFZ^*COORi and -CFZ*-CH₂(OCH₂CH₂)_k-OH, wherein k is ranging from 0 to 10, wherein Z* is F or CF3; Ri is a C₁-C6 hydrocarbon chain; and (ii) (hydro)(fluoro)carbon groups comprising at least an anthracene moiety

(anthracene group) of formula (II):

wherein

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

Claim 4. The monomer of any one of claims 1-3, wherein n in formula (II) equals 0.

Claim 5. The monomer of any one of claims 1-4, wherein R_fa is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (VII):

(CFXi)_a O(Rh)(CFX₂)b (VII)

wherein

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

- Xi and X₂, independently form each other, are F or CF₃, provided that when a and/or b are higher than 1 , X₁ and X₂ are F;

(i) -CFX₁O-, wherein X₁ is F or CF3;

(ii) -CFX₁CFX₁O-, wherein X₁ , equal or different at each occurrence, is F or CF3, with the proviso that at least one of X₁ is F;

(iii) -CF₂CF₂CW₂0-, wherein each W is independently from each other, F, Cl or H;

(iv) -CF₂CF₂CF₂CF₂0-;

(v) -(CF₂)_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 CFX1O , CF2CFX1O, CF2CF2CF2O, CF2CF2CF2CF2O, wherein each Xi is independently from each other F or CF3 and T is a C1-C3 perfluoroalkyl group.

Claim 6. The monomer of any one of claims 1-4, wherein R_fa is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of

formula (VIII):

X¹ is, independently at each occurrence, F or CF3,

- X² and X³, independently from each other and at each occurrence, are F or CF3, with the proviso that at least one of X is F;

Claim 7. The monomer of any one of claims 1-4, wherein R_fa is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (IX):

[ (CF₂0)_n (CF₂CF₂0)_m ]_p (IX)

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.

Claim 8. The monomer of any one of claims 1-4, wherein R_fa is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (X):

-[(CF₂CF₂0)bi (CF₂0)b2(CF(CF3)0)b3(CF2CF(CF₃)0)b4]- (X) 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.

Claim 9. The monomer of any one of claims 1-4, wherein R_fa is a fluorinated polyether comprising at least one fluoropolyether (PFPE) chain of formula (XI): -[(CF2CF20)CI (CF20)C2(CF2(CF2)CWCF₂0)C3]- (XI)

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.

Claim 10. A process for manufacturing the monomer of any one of claims 1-9, comprising the reaction of anthracene, possibly substituted with R_n, with a compound of formula (XIV):

X-CF₂-R_fa-T^c (XIV)

wherein

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

R_fa is a fluorinated (co)polymer;

T^c is selected from the group consisting of:

(ii) CF₂-X.

Claim 11. An adduct obtained from exposing at least the monomer of any one of claims 1-8 to UV light at a wavelength ranging from 280 nm to 600 nm, preferably from 300 nm to 450 nm.

Claim 12. A polymer blend comprising at least 1 mol.% of monomers according to any one of claims 1 -9.

Claim 13. A process for coating a surface, comprising:

a) applying to the surface the monomer of any one of claims 1-9 or the polymer blend of claim 12, and

Claim 14. A process for manufacturing a shaped article, comprising:

a) applying to a mould the monomer of any one of claims 1-9 or the polymer blend of claim 12, and

Claim 15. A process for recycling a coating or a shaped article comprising the polymer adduct of claim 11 , by a) exposing the coating or the shaped article to UV light at a wavelength of less than 300 nm, b) heating the coating or the shaped article at a temperature higher 180°C, preferably higher 195°C, or c) exposing the coating or the shaped article to microwave radiation.