WO2013118100A2

WO2013118100A2 - Process for the treatment of a polymer

Info

Publication number: WO2013118100A2
Application number: PCT/IB2013/051068
Authority: WO
Inventors: Massimo Benaglia
Original assignee: Consiglio Nazionale Delle Ricerche
Priority date: 2012-02-10
Filing date: 2013-02-08
Publication date: 2013-08-15
Also published as: EP2812363A2; WO2013118100A3; ITBO20120066A1

Abstract

Process for the treatment of a polymer or copolymer of poly (glycidyl methacrylate ) (PGMA); the process comprises reacting the polymer with a nucleophile selected from secondary amines, thiols and aromatic alcohols in the presence of an aprotic polar solvent having an oxygen capable of forming hydrogen bridges; the use of this solvent allows linear. homopolymers and linear block copolymers to be obtained under particularly efficient conditions. An additional treatment is also envisaged for introducing functionalities on the hydroxyl deriving from the opening of the epoxy ring. Finally, a controlled hyper-branching treatment is envisaged for obtaining nano-structured material.

Description

PROCESS FOR THE TREATMENT OF A POLYMER

TECHNICAL FIELD

The present invention relates to a process for the treatment of a polymer.

CONTEXT OF THE INVENTION

As polyglycidyl methacrylate (PGMA) is composed of monomeric units carrying epoxy groups, it is suitable for transformation processes that involve the opening of oxyrane rings on the part of various nucleophilic agents. The nucleophilic reagent binds itself to the least substituted carbon of the epoxy ring and through a reaction of the SN² type, leads to the formation of a hydrox l group.

Although this reaction is easily accessible when applied to small molecules, it becomes difficult when effected on a polymeric substrate. The first difficulty lies in obtaining an exhaustive reaction involving all the epoxy groups present in the chain.

A second difficulty, which is equally important, can be attributed to the high reactivity of the glycidyl residues that leads to hyper-branched polymeric chains with the formation of insoluble material in gel form. With respect to epoxy groups, there is a wide range of active nucleophilic reagents, among these amines.

Attempts have been made at effecting ring-opening reactions with primary amines. These, however, can lead to the formation of secondary amines that can further react with other epoxy groups. Consequently, when operating on a polymeric substrate, an intrachain reaction can take place with the formation of a macrocycle, or an interchain reaction when the secondary amine formed reacts with a glycidyl group of another chain thus leading to the formation of a branching. This process however is difficult to control as it easily leads to the formation of an insoluble macro-gel which is the result of the random connection of numerous polymeric chains through amine bridges.

Possible uses of derivatives of the polymers indicated above are in the field of bio- nanotechnologies, for example for "drug delivery", "gene delivery", diagnostics.

An example of a possible use is producing micelles that can carry, in their interior, substances for therapeutic and/or diagnostic use.

There is therefore the obvious necessity of providing an effective process for the treatment of polymers carrying one or more glycidyl residues, which does not have the drawbacks of the known art for leading to the formation of linear chains of homopolymers and block copolymers and which, at the same time, is possibly easy and economical to effect.

These objectives are achieved by means of the process of the present invention, as described hereunder .

SUMMARY

According to the present invention, a process is provided for the treatment of a polymer and a polymer according to what is specified in the following independent claims and, preferably, in any of the claims depending directly or indirectly on the independent claims .

Unless the contrary is explicitly specified, the following terms have the meaning indicated hereunder.

In the present text "C_x-C_y" refers to a group having from x to y carbon atoms .

In the present text "aliphatic" refers to a non- aromatic and non-substituted hydrocarbon (unless the contrary is specified) , saturated or unsaturated, linear, branched and/or cyclic. Non-limiting examples of aliphatic groups are: t-butyl, ethenyl, 1- or 2- propenyl, cyclohexyl.

In the present text "alkyl" refers to a saturated aliphatic compound (i.e. an aliphatic group without double or triple carbon-carbon bonds) . Non-limiting examples of alkyls are: methyl, n-propyl, t-butyl, cyclohexyl .

In the present text "alkenyl" refers to an unsaturated aliphatic compound having at least one double carbon-carbon bond and without triple carbon- carbon bonds .

In the present text "aromatic group" refers to a group having at least one aromatic ring, in particular containing from 5 to 12 members and a substantially conjugated π electronic system. In particular, the aromatic group comprises a monocyclic ring or various condensed rings (i.e. rings that share a pair of adjacent and bound atoms) . Each aromatic ring can be arylic (i.e. in which all the members of the ring are carbon atoms) or heteroaromatic (i.e. in which one, or two or three of the members of the ring are selected from N, 0, S; the remaining members of the ring are carbon atoms) . Non-limiting examples of aromatic groups are: phenyl, naphthenyl, anthracenyl, pyrrole, furane, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrimidine, purine and carbazole.

The term "aryl" as used in this text, indicates an aromatic group, in which each aromatic ring is arylic. Examples of aryls are: naphthalene and phenanthrene.

In the present text, "aromatic heterocycle" refers to an aromatic group in which at least one aromatic ring is heteroaromatic. Examples of aromatic heterocycles are: pyrrole, furane, thiophene, pyridine, indole .

EMBODIMENTS OF THE INVENTION

According to a first aspect of the present invention, a process is provided for the treatment of a polymer containin at least one group having formula I:

wherein the carbon of the carboxylic function is connected to the remaining part of the polymer;

the process comprises a first reaction phase, during which the polymer reacts with a nucleophile (H- Nu or Nu^~) in the presence of an organic solvent so that the group having formula I is modified so as to have formula II:

Heat is advantageously supplied during the first reaction phase. In particular, the first reaction phase takes place at a temperature ranging from 30 °C to 250°C. In some cases, the reaction phase takes place at a temperature of at least 50°C (more specifically, at least 70°C). According to some embodiments, the reaction phase takes place at a temperature of up to 150°C (more specifically, up to 100°C) .

The heat is advantageously supplied for a period of time ranging from 15 minutes to 16 hours and, even more advantageously, ranging from 30 minutes to three hours.

The nucleophile is advantageously used in excess with respect to the groups having formula I. In particular, the molar ratio between the nucleophile and the groups having functionality I ranges from 1.1 to 10. In some cases, the molar ratio between the nucleophile and the groups having functionality I is at least 1.5 (more specifically at least 1.9).

The organic solvent is aprotic, it has a dipole moment higher than 0 and at least one oxygen atom. In particular, the oxygen atom is capable of effectively binding itself through a hydrogen bridge.

It has been experimentally observed that, by using a solvent as defined above, the modified group is surprisingly obtained under relatively bland conditions and with high yields (in many cases quantitative) .

More specifically, a solvent is considered aprotic when it does not have a hydrogen atom bound to an oxygen atom or nitrogen atom.

It should be noted that it has been experimentally observed that the characteristics (in particular, the aproticity and presence of an oxygen atom) of the solvent are extremely important for obtaining an efficient reaction phase. The use of protic solvents, such as, for example, ethyleneglycol monobutyl ether, can lead to transesterification reactions with the formation of insoluble material due to uncontrolled branchings .

These uncontrolled reactions do not take place, on the contrary, using aprotic solvents containing oxygen, as demonstrated in the experimental part of the present invention .

In particular, it has also been observed that the results are particularly good when the solvent has a dipole moment higher than 3.5 (in particular, higher than 3.7).

According to some embodiments, the organic solvent comprises (more specifically, is) a solvent selected from the group consisting of: D SO (dimethylsulfoxide) , Dimethylformamide, Dimethylacetamide, Dioxane, THF ( tetrahydrofuran) , Acetone, Ethyl acetate, Methyl acetate, 1, 3-Dimethyl-2-imidazolidinone, Nitromethane, Nitroethane, Sulfolane, N-Methylpyrrolidone, Propylene carbonate, Hexamethylphosphorictriamide , diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, nitrobenzene. In particular, the organic solvent comprises (more specifically, is) a solvent selected from the group consisting of: DMSO, Dimethylformamide, Dimethylacetamide, Dioxane, Acetone, Ethyl acetate, Methyl acetate, 1 , 3-Dimethyl-2-imidazolidirtone , Nitromethane, Nitroethane, Sulfolane, N-

Methylpyrrolidone, Propylene carbonate, Hexamethyl- phosphorictriamide, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, Nitrobenzene.

The organic solvent advantageously comprises (more specifically, is) a solvent selected from the group consisting of: DMSO, Dimethylformamide,

Dimethylacetamide, 1, 3-Dimethyl-2-imidazolidinone, Nitromethane, Nitroethane, Sulfolane, N-Methyl- pyrrolidone, Propylene carbonate, Hexamethylphosphorictriamide . More specifically, the organic solvent comprises (more specifically, is) a solvent selected from the group consisting of: DMSO, Dimethylformamide, Dimethylacetamide, 1, 3-Dimethyl-2- imidazolidinone, Sulfolane, N-Methyl-pyrrolidone,

Propylene carbonate, Hexamethylphosphorictriamide. In specific cases, the organic solvent comprises (more specifically, is) DMSO.

The nucleophile (H-Nu, Nu^~) is advantageously selected from the group consisting of: secondary amine, thiol and aromatic alcohol, in which a hydroxyl group is directly bound to an aromatic ring, anionic reagent.

According to some embodiments, the anionic reagent is selected from the group consisting of: azides, thiocyanate .

The nucleophile (H-Nu, Nu^~) is advantageously selected from the group consisting of: secondary amine, thiol and aromatic alcohol, in which a hydroxyl group is directly bound to an aromatic ring.

In particular, the secondary amine is not of the group consisting of:

According to some embodiments, the secondary amine is C₂-Ci4 (more specifically, C₂-C8) .

More specifically, the secondary amine is cyclic. In some cases, the secondary amine has the formula HNR¹]^² (III), wherein R¹ and R² are each independently selected from the group consisting of: Ci-C₇ alkyl, Ci~C₇ alkenyl with from 1 to 3 double bonds. Optionally, R¹ comprises from 1 to 2 oxygen atoms (each of which is ether or hydroxyl) . Optionally, R¹ comprises from 1 to 3 nitrogen atoms, each of which (independently) is tertiary (or secondary) .

Optionally, R² comprises from 1 to 2 oxygen atoms

(each of which is ether or hydroxyl) . Optionally, R² comprises from 1 to 3 nitrogen atoms, each of which (independently) is tertiary (or secondary).

Optionally, R¹ and/or R² comprise from 1 to 2 halogens (as substituent of alkyl or alkenyl) .

In particular, ether oxygen refers to an oxygen forming part of an ether functionality, i.e. an oxygen bound to two carbon atoms. Hydroxyl oxygen refers to an oxygen forming part of a hydroxyl functionality, i.e. bound to a hydrogen. A secondary nitrogen is a nitrogen bound to only one hydrogen. A tertiary nitrogen is not bound to any hydrogen.

Optionally, R¹ and R² are bound to each other so as to form from 1 to 3 cycles. Each cycle can be aromatic.

In particular, the secondary amine is selected from the group consisting of: morpholine, piperidine, 4- hydroxypiperidine, 3-hydroxypiperidine , 2— hydroxypiperidine, N-methylpiperazine, methyl ethanolamine, diethanolamine, imidazole, benzimidazole, triazole, carbazole, purine, uracyl, thymine.

In some cases, the secondary amine is selected from an aromatic heterocycle (non-substituted) , HNR¹R² and

In particular, the secondary amine (aromatic heterocycle) is selected from the group consisting of: imidazole, benzimidazole, triazole, carbazole, purine, uracyl, thymine.

In addition or alternatively, in particular, R¹ and R² (are not bound to each other so as to define a ring) and each independently represent Ci-C₆ aliphatic groups (linear) having from 1 to 3 substituents selected from the group consisting of: OH, halogen, carbonyl, ester, tertiary amine, nitrile, nitro, sulfide. In particular, the substituents are selected from the group consisting of: OH, halogen, nitrile, nitro. More specifically, the substituent is OH (or halogen) .

In addition or alternatively, in particular, in formula X:

E is selected from the group consisting of: 0, N, CH; X¹, X², X³, X⁴, X⁵ are each independently selected from the group consisting of: Ci-C₂ aliphatic (in particular linear, in particular, alkyl) , OH, H, halogen, carbonyl, ester, tertiary amine, nitrile, nitro, sulfide; on the condition that, when E is an oxygen, X³ is not present; on the condition that, when E is a nitrogen, X³ is selected from Ci-C₂ aliphatic (in particular linear; in particular, alkyl), and H.

In particular, X¹, X², X³, X⁴, X⁵ are each independently selected from the group consisting of: Ci- C₂ aliphatic (in particular linear, in particular, alkyl), OH, H, halogen. More specifically, X¹, X², X³, X⁴, X⁵ are each independently selected from the group consisting of: C1-C2 aliphatic (in particular linear, in particular, alkyl) , OH, H. In some cases, at least 3 (more specifically, at least 4) of X¹, X², X³, X⁴, X⁵ are H.

According to some embodiments, the thiol is Ci-C₂6 (in particular, C1-C10) ·

The thiol can be an aromatic group (more specifically, an aryl) or aliphatic group (substituted or non-substituted) (or a combination thereof) having (at least) one SH functionality. The thiol advantageously only has one SH functionality.

More specifically, in some cases, the thiol is an aliphatic group (substituted or non-substituted) having (at least) one SH functionality. More specifically, the thiol is a linear alkyl (substituted or non- substituted) having (at least) one SH functionality.

In some cases, the thiol is an aromatic group (more specifically, an aryl) having (at least) one SH functionality.

According to some embodiments, the thiol comprises (in addition to SH) from 1 to 3 substituents selected from the group consisting of: OH, halogen, carbonyl, ester, tertiary amine, nitrile, nitro, sulfide. In particular, the substituents are selected from the group consisting of: OH, halogen, nitrile, nitro. More specifically, the substituent ( s ) is/are OH (or halogen) . According to specific embodiments, the thiol comprises only one substituent (in addition to SH) .

In some cases, the aliphatic compound (more specifically, the alkyl) of thiol is linear.

According to some embodiments, the aromatic alcohol is Ci-C₂6 (in particular, Ci-Ci₈; more specifically, Ci- C14) .

In particular, the aromatic alcohol is an aromatic group having (at least) one OH functionality.

In some cases, the aromatic alcohol is an alcohol of one of the following aromatic groups: furane, thiophene, imidazole, pyrimidine, quinoline, isoquinoline, indole, purine, benzene naphthalene, anthracene, phenanthrene, pyrene, benzopyrene. In particular, the aromatic alcohol is an alcohol of one of the following aromatic groups: furane, thiophene, benzene naphthalene, anthracene, phenanthrene, pyrene, benzopyrene, triphenylene, coronene, hexahelicene .

Advantageously, the aromatic alcohol does not comprise further substituents (in addition to -OH) . The thiol advantageously has only one OH functionality.

In some cases, the polymer comprises glycidyl methacrylate units copolymerized with other monomers.

In particular, the polymer comprises at least one chain block of poly (glycidyl methacrylate) (PGMA). The group with formula I (more specifically) formula la:

The polymer can be a PGMA homopolymer or a PGMA copolymer. The polymer therefore has the following chain or chain block)

The PGMA can be obtained by means of conventional radical polymerization. The polymer is advantageously ' obtained by means of controlled polymerization (radical) techniques. Among these, RAFT (Reversible

Addition-Fragmentation chain Transfer) [WO9801478 or Atom Transfer Radical Polymerization (ATRP) [US6071980 (A)] o Nitroxide Mediated radical Polymerization (NMP) [EP0135280 (A2)], can be mentioned. The use of polymers synthesized by means of controlled polymerization techniques which therefore have a predetermined molecular weight and with a narrow distribution facilitates their reaction operations and subsequent identification. With these techniques, it is also possible to easily obtain block copolymers. In particular, the RAFT technique can allow the introduction of specific functionalities at the head and tail of the polymeric chains.

A further treatment is also envisaged for the introduction of functionalities on the hydroxyl deriving from the opening of the epoxy ring.

Finally, a controlled hyper-branching treatment is envisaged for obtaining nano-structured material.

According to a second aspect of the present invention, a further process is provided for the treatment of a polymer containing at least one group having formula II as defined above (and wherein the carbon of the carboxylic function is bound to the remaining part of the polymer) .

Analogously to what is specified with respect to the first aspect of the invention, the polymer is, according to some embodiments, a derivative of PGMA. In these cases, the group having formula II has (more specifically) formula Ila:

The polymer can be a homopolymer of PGMA or a copolymer of PGMA.

The polymer is advantageously obtained by means of controlled polymerization (radical) techniques.

This process comprises an addition phase. The addition is to the hydroxyl of a group having formula (II) (or Ila) .

According to some embodiments, during the addition to the hydroxyl of the group having formula II, isocyanate R-NCO is added; the group having formula II is modified so as to have formula IV:

(IV). According to some embodiments, during the addition to the hydroxyl of the group having formula II, X-Y or K-Z is added. X is selected from the group consisting of CI, Br. Y is selected from the group consisting of: -COR, -C(0)0R, -P(O) (OR) 2 , -S(0)₂OR; K and Z each indicate -OC(0)R.

When the addition phase is effected with X-Y, the group having formula II is modified so as to have formula V:

When the addition phase is effected with X-Y, the group having formula II is modified so as to have formula VI:

(VI) .

R indicates a substituent, in particular Ci-Cio, selected from the group consisting of: aliphatic groups (optionally substituted) , aromatic groups (optionally substituted) and a combination thereof.

The object of the first and second aspect of the present invention can be combined. In these cases, the addition phase advantageously follows (at least partially) the first reaction phase.

Alternatively or in addition to the first aspect of the present invention, in accordance with a third aspect of the present invention, a process is provided for the treatment of a polymer containing at least one group having formula I as defined above (and wherein the carbon of the carboxylic function is bound to the remaining part of the polymer) . The process comprises a reaction phase, during which the nucleophile reacts with the group having formula I or (la) as indicated with respect to the first aspect of the present invention. The nucleophile is defined in accordance with the first aspect of the present invention.

The nucleophile is advantageously an anionic reagent .

The anionic reagent (A) reacts with the group having formula I (or la) so as to obtain the group havin formula VII:

Heat is advantageously supplied during the reaction phase. In particular, the reaction phase takes place at a temperature ranging from 30°C to 250°C. In some cases, the reaction phase takes place at a temperature of at least 50°C (more specifically, at least 70°C). According to some embodiments, the reaction phase takes place at a temperature of up to 150 °C (more specifically, up to 100°C).

The nucleophile is advantageously used in excess with respect to the groups having formula I. In particular, the molar ratio between the anionic reagent and groups having functionality I ranges from 1.1_. to 10. In some cases, the molar ratio between the anionic reagent and the groups having functionality I is at least 1.5 (more specifically, at least 1.9).

In particular, the polymer comprises at least one block of the poly (glycidyl methacrylate) (PGMA) chain. The group with formula I having (more specifically) formula la:

The polymer can be a PGMA homopolymer or a PGMA copolymer.

The reaction phase of the third aspect of the invention is carried out with a solvent as defined according to the first aspect. More generally, what is described for the first aspect also applies to the third aspect.

According to some embodiments, the anionic reagent is selected from the groups consisting of: azide, thiocyanate.

The object of the first and third aspect of the present invention can be combined. In these cases, the reaction phase of the third aspect advantageously follows (at least partially) the reaction phase of the first aspect. At the end of the reaction phase of the first aspect, the polymer comprises at least one group having formula I. In these cases, the nucleophile used in the first reaction phase of the first aspect of the present invention is advantageously different from the nucleophile of the reaction phase of the third aspect of the invention.

In this way, a polymer can be obtained with parts functionalized in different ways. An example of this is illustrated in the followin reaction scheme:

According to a fourth aspect of the present invention, a further process is provided for the treatment of a polymer containing at least one group having formula II as defined above (and wherein the carbon of the carboxylic function is bound to the remaining part of the polymer) .

Analogously to what is specified for the first aspect of the invention, according to some embodiments, the polymer is a derivative of PGMA. In these cases, the group having formula II has (more specifically) formula Ila:

The polymer can be a derivative of a PGMA homopolymer or a PGMA copolymer.

This process comprises a controlled crosslinking phase, during which two groups having formula II (or Ila) react with each other so as to obtain the formation of ester bridges having formula VIII:

(VIII) In particular, the groups having formula II that react with each other are of two distinct polymeric chains.

The crosslinking phase advantageously takes place in the presence of water. In particular, the crosslinking phase takes place under dialysis conditions in which the polymer is confined in a semipermeable membrane tube with a porosity that is such as to keep the polymeric material separate. This process is autocatalytic in the case of polymers deriving from treatment with amines, or it can also be catalyzed in an acid environment.

According to some embodiments, the crosslinking phase takes place at a temperature of at least 40°C (in particular, up to 100°C) . The reaction phase advantageously takes place at a temperature of at least 60°C. In particular, the reaction phase takes place at a temperature of up to 90°C (more specifically, at about 80°C) .

The object of the first and fourth aspect of the present invention can be combined. In these cases, the crosslinking phase advantageously follows (at least partially) the reaction phase of the first aspect. At the end of the reaction phase of the first aspect, the polymer comprises at least one group having formula I. In some cases, at the end of the reaction phase of the first aspect, the polymer comprises at least two groups having formula I .

According to a further aspect of the present invention, a polymer is provided having at least one group having the formula (according to what is described above) selected from the group consisting of: formula II, formula IV, formula V, formula VI, formula VII, formula VIII.

More specifically, in the above-mentioned formulae (in particular, II, IV, V and VI) Nu corresponds to the nucleophile indicated with respect to the first aspect of the present invention without the possible counterion (for the anionic reagents) and/or hydrogen (bound to the heteroatom (N, S, 0) , which is bound to the polymer) .

Analogously to what is specified with respect to the first aspect of the invention, according to some embodiments, the polymer is a derivative of PGMA. In these cases, the group having formula II has (more specifically) formula Ila:

What is indicated with respect to the first aspect of the invention also applies to the fourth aspect mutatis mutandis .

The polymer can be a PGMA homopolymer or a PGMA copolymer .

The polymer is advantageously obtained by means of controlled (radical) polymerization techniques.

Unless the contrary is explicitly indicated, the content of the references (articles, books, patent applications, etc.) cited in this text is an integral part thereof. In particular, the above references are incorporated herein as reference.

Further features of the present invention will appear evident from the following description of two examples provided for purely illustrative and non- limiting purposes.

Examples

The following materials and instruments were used in the examples provided hereunder:

2-Cyano-2-propanyl dithiobenzoate (RAFT 1) [Tetr. Lett. 1999, 40, 2435]; 2 , 2 ' -azobis (2 , -dimethylvalero nitrile) [DuPont] ; azobis (isobutyronitrile) (AIBN) , azobis ( 1-cyanocyclohexane ) , glycidyl methacrylate

(GMA) , methyl methacrylate (MMA) , styrene (St), butyl acrylate (BA) , N-phenyl maleimide, N-methyl maleimide, morpholine, piperidine, 4-hydroxypiperidine, 3- hydroxypiperidine, N-methylpiperazine, methyl ethanolamine, diethanolamine, imidazole, benzimidazole, sodium azide, 2-mercaptoethanol , phenol, phenyl isocyanate, triethylamine, dimethyl sulfoxide (DMSO) , chloroform, ethyl ether, cyclohexane [Sigma-Aldrich] . NMR Spectrometer Varian Mercury 400; Gel Permeation chromatography GPC - MSI Concept PU III equipped with Refractive Index Detector - Shodex RI-71, GPC PL mixE column, calibration standard of polystyrene Polymer Laboratory; Spectrometer FT/IR Perkin Elmer BX.

Example 1

Synthesis of the RAFT agent 2-cyano-4-methylpentan- 2-yl diethoxyphosphonodithioformiate (RAFT 2)

The procedure described in J. Org. Chem. 2002, 67, 7911-7914 of . Benaglia, A. Alberti, M. Laus, K. Sparnacci was followed.

A solution was prepared, containing 1.41 g of triphenylmethyl diethoxyphosphoryldithioformiate and 0.57 g of 2 , 2-azobis (2 , 4-dimethylvaleronitrile) in 50 ml of benzene.

The solution was deoxygenated before being refluxed under a nitrogen atmosphere for 16 hours. After the removal of the solvent, the raw product was subjected to chromatography on silica gel, using ethyl ether/dichloromethane 95/5, as eluent. 0.85 g of product were obtained (yield 85%) . ¹H-NMR (400 MHz, CDC1₃), δ: [1.05 (d, J = 6.8 Hz, 3H) ; 1.12 (d, J = 6.4 Hz, 3H) (CH(CH₃)₂) ] ; 1.36 (t, J = 7 Hz, 6H) (OCH₂Cff₃) ; [1.81 (dd, ¹J = 14 Hz, ²J = 5.6 Hz, 1H) ; 2.10 (dd, ¹J = 14 Hz, ²J = 6 Hz, 1H) (Cff₂) ] ; 1.87 (s, 3H, C(CH₃)CN); 2.01 (m, 1H, CH₂CHMe₂) ; 4.23 (m, 4H) , (OCH₂CH₃) . ¹³C-NMR

(100 MHz, CDC1₃), <5: 16.09, 16.15 (OCH₂CH₃) ; 23.34 (C(CH₃)CN); 23.79, 24.03 (CH(CH₃)₂); 25.55 (CH₂CHMe₂) ; 45.64, 45.70 ( MeCN) ; 46.21 (CH₂) ; 64.95, 65.02

(OCH₂CH₃) ; 117.91 (C ) ; 224.64, 226.34 (OS).

Example 2

Synthesis of the RAFT agent 2-cyano-4-methylpentan- 2-il 4-cyanodithiobenzoate ( RAFT 3 )

procedure described Macromolecules 2005, 3826-, 7911-7914 of M. Benaglia, E. Rizzardo, A. Alberti, M. Guerra was followed.

A solution was prepared, containing 100 mg of bis (4- cyanothiobenzoyl ) disulfide and 80 mg of 2,2'- azobis (2 , 4-dimethylvaleronitrile) in 20 ml of benzene. The solution was deoxygenated before being refluxed under a nitrogen atmosphere for 16 hours. After the removal of the solvent, the raw product was subjected to chromatography on silica gel, using dichloromethane as eluent. 153 mg of product were obtained (yield 95%) ¹H-NMR (400 MHz, CDC1₃) , <5: [1.08 (d, J = 6.4 Hz, 3H) ; 1.12 (d, J = 6.8 Hz, 3H) (CH (Cff₃) ₂) ] ; [1.88 (dd, ¹J = 14.2 Hz, ²J = 5.8 Hz, 1H) ; 2.21 (dd, ¹J = 14.2 Hz, ²J = 6.6 Hz, 1H) (C¾)]; 1.96 (s, 3H, C(CH₃)CN); 2.07 (m, 1H, CH₂CflMe₂) ; 7.67 (d, J = 8.4 Hz, 2H, o-Arff) ; 7.92 (d, J = 8.4 Hz, 2H, m-Arfl) . ¹³C-NMR (100 MHz, CDC1₃) , <5: 23.51, 23.98 (CH(CH₃)₂); 24.57 (C(CH₃)CN); 25.77 (CH₂CHMe₂) ; 46.37 ( MeCN); 46.61 (CH₂) ; 115.60 (ArC-4) ; 117.89 (ArCN) ; 118.79 (CMeCN); 127.11 (ArC-2); 132.31 (ArC-3) ; 147.30 (ArC-1); 220.41 (OS).

Example 3

Synthesis of poly (glycidyl methacrylate

A mother solution containing glycidyl methacrylate,

RAFT agent, AIBAN and toluene was prepared. This solution was poured into ampoules equipped with a vacuum seal valve to allow its deoxygenation by 4 freezing-vacuum-defrosting cycles. The ampoules were then placed in a thermostatic bath at 70°C for the established time. The polymerization was stopped after cooling and the polymer precipitated from ethyl ether. NMR and GPC analyses were effected. ¹H-N R (400 MHz, CDCI₃) , δ: 0.92, 1.10, 1.9-2.1 (H chain) ; 2.65, 2.85 ( H 3); 3.22 (H 2); 3.80, 4.30 (H I)

Various tests were carried out following this procedure, of which the conditions and results are respectively indicated in Table 1 and in Table 2 hereunder .

Table 1

Table 2

^a = gravimetric conversion, ^b = NMR conversion

The molecular weight (Mn) and PDI were revealed by means of GPC in THF at 25°C.

Example 4

Synthesis of poly (glycidyl methacrylate) -b-poly (methyl methacr late

A mother solution was prepared, containing 7 ml of MMA, 1.13 g of macro-RAFT poly ( glycidyl methacrylate) [from example 3(l)b], 0.44 mg of AIBN and acetonitrile up to a total volume of 10 ml. This solution was poured into an ampoule equipped with a vacuum seal valve to allow its deoxygenation by means of 4 freezing-vacuum- defrosting cycles. The ampoule was then placed in a thermostatic bath at 70 °C for 5 hours. The polymerization was stopped after cooling and the volatile component of the solution containing the polymer was removed under vacuum in a rotating evaporator. A conversion of 27.7% was obtained. NMR and GPC analyses were effected. GPC in THF at 25 °C Mn = 47300 PDI = 1.1 ¹H-NMR (400 MHz, CDC1₃) , <5: 0.76-1.14, 1.72-2.10 ( H chain); 2.63, 2.83 (A3); 3.22 (H2) ; 3.59 {HA) ; 3.80, 4.29 (HI) .

Example 5

Synthesis of poly ( glycidyl methacrylate) -b-polystyrene

A mother solution was prepared, containing 6 mL of styrene, 0.8 g of macro-RAFT poly (glycidyl methacrylate) [from example 3(l)b], 1.3 mg of azobis(l- cyanocyclohexane and acetonitrile up to a total volume of 10 mL. This solution was poured into an ampoule equipped with a vacuum seal valve to allow its deoxygenation by means of 4 freezing-vacuum-defrosting cycles. The ampoule was then placed in a thermostatic bath at 90 °C for 4 hours and 30 minutes. The polymerization was stopped after cooling and the volatile component of the solution containing the polymer was removed under vacuum in a rotating evaporator. A conversion of 7.7% was obtained . NMR and GPC analyses were effected. GPC in THF at 25 °C Mn = 39000 PDI = 1.25 ^H-NMR (400 MHz, CDC1₃) , <5: 0.80-1.20, 1.20-1.63, 1.64-2.18 (H chain) ; 2.62, 2.82, (H3) ; 3.21 (HZ); 3.80, 4.30 (HI); 6.25-6.84, 6.85-7.22 (HPh) .

Example 6

Synthesis of poly (glycidyl methacrylate) -b-poly (butyl

A mother solution was prepared, containing 4.7 mL of butyl acrylate, 0.58 g of macro-RAFT poly (glycidyl methacrylate) [from example 3(l)b], 0.23 mg of AIBN and acetonitrile up to a total volume of 10 mL. This solution was poured into an ampoule equipped with a vacuum seal valve to allow its deoxygenation by means of 4 freezing-vacuum-defrosting cycles. The ampoule was then placed in a thermostatic bath at 70°C for 2 hours. The polymerization was stopped after cooling and the polymer was precipitated in methanol. A conversion of 15% was obtained. NMR and GPC analyses were effected. GPC in THF at 25 °C Mn = 47000 PDI = 1.16 ^^"H-NMR (400 MHz, CDCI₃) , δ: 0.93, ( CH2CH2CH2CH3 ) ; 0.92, 1.09, 1.80- 2.08, 2.18-2.40, (H chain); 1.36 (CH₂CH₂CH₂CH₃) ; 1.60 ( CH2CH2CH2CH3 ) ; 2.65, 2.85 (A3); 3.22 (H2); 3.80, 4.30 (HI) ; 4.03 ( OCH2CH2CH2CH3 ) .

Treatment of homo- and copolymers of PGMA with nucleophiles

The basic methods followed in the subsequent examples are described hereunder.

Treatment with amines

a) without functionalization of the freed -SH end. PGMA [from example 3(2)d] was dissolved in DMSO, the amine was added to this solution in such a quantity as to reach a concentration equal to 2 moles/L. The mixture was heated to 80 °C for 2 hours unless otherwise specified. The volatile component was removed in a rotating evaporator at a pressure of about 1 Torr. Precipitation was effected, when necessary, by dripping a polymer solution into a suitable solvent. NMR and GPC analyses were carried out.

b) with functionalization of the freed -SH end.

PGMA [from example 3(2)d] was dissolved in DMSO, the solution was deoxygenated by bubbling nitrogen for 15 minutes. Two equivalents of amine were added (calculated on the basis of the molecular weight of the polymer) and left under stirring for thirty minutes. Two equivalents of N-phenyl maleimide (3.2 mg calculated on the basis of the molecular weight of the polymer) were then added, care being taken to keep the reaction mixture deoxygenated and the mixture was left to react for two hours. The amine was subsequently added in such a quantity as to have a concentration of 2 moles/L, the mixture was heated to 80°C for 2 hours. The volatile component was removed in a rotating evaporator at a pressure of about 1 Torr. Precipitation was effected, when necessary, by dripping a polymer solution into a suitable solvent. NMR and GPC analyses were carried out.

Example 7

Treatment with morpholine

polymer +

Method (a) 100 mg of PGMA in 2.5 mL of DMSO with 0.52 mL of morpholine. Heating to 80°C for 30 minutes. The polymeric material obtained was then dissolved using method (a) in chloroform and was precipitated in cyclohexane.

The transformation (in this example as also in the others, unless otherwise specified) takes place quantitatively as revealed by NMR analysis.

¹H-NMR (400 MHz, CDCI3) : 5_{[ ch}ioroform-d] : 0.92, 1.07, 1.7-2.1 (H chain); 2.44, 2.65 (H3) ; 2.51 (HA) ; 3.74 (H5) ; 2.88, 4.01 {HI) ; 4.01 (H2) . GPC (THF; 25°C) Mn 14400; PDI 1.18

Example 8

Treatment with morpholine polymer +

Method (b) 100 mg of PGMA in 2.5 mL of DMSO with 1.6 μΐ, of morpholine as first addition and 0.52 mL as second addition. Heating to 80°C for 30 minutes.

The polymeric material obtained was then dissolved using method (b) in chloroform and then precipitated in cyclohexane.

NMR as for example 7.

Example 9

Treatment with morpholine

polymer +

20 mg of PGMA were dissolved in DMS0-d₆ and 12.3 of morpholine (1 equivalent with respect to the glycidyl units) were added; the solution was placed in a NMR tube. It was heated in an oil bath to 80°C and the conversion was followed by means of NMR, removing the tube from the bath at pre-established times. After 31 hours of heating, the conversion of the opening reaction of the glycidyl groups proved to be equal to 90%.

NMR as in example 7.

Example 10 (comparative; with solvent having a low bipole moment)

Treatment with morpholine in the presence of dioxane

polymer +

100 mg of PGMA [from example 3(2)d] were dissolved in 2.5 mL of dioxane. 0.52 mL of morpholine were then added and the solution was heated to 80 °C for 2 hours. The volatile component was removed in a rotating evaporator at a pressure of about 1 Torr. NMR analysis revealed an incomplete conversion of the glycidyl groups ..

Example 11 (comparative: with protic solvent)

Treatment with morpholine in the presence of ethylene glycol monobutyl ether

polymer +

100 mg of PGMA [from example 3(2)d] were dissolved in 2.5 mL of ethylene glycol monobutyl ether. 0.52 mL of morpholine were then added, and the solution was heated to 80°C for 16 hours. The formation of hyper- branched insoluble material was observed.

Example 12

Treatment of PGMA with morpholine and sodium azide

100 mg of PGMA [from example 3(2)d] were dissolved in 2.5 mL of D SO, the solution was deoxygenated by bubbling nitrogen for 15 minutes. 1.6 μΐ, of morpholine were added and the mixture was left under stirring for 30 minutes. 3.2 mg of N-phenyl maleimide were then added, care being taken to keep the reaction mixture deoxygenated, and the mixture was left to react for 2 hours. 123 μΐ. of morpholine were then added, and the whole mixture was heated to 80 °C for 2 hours. 4 μΐ, of glacial acetic acid were added and subsequently 4.6 mg of NaN₃, the mixture was left to react at 80°C for a further two hours. The volatile component was removed in a rotating evaporator at a pressure of about 1 Torr. The polymeric material was dissolved in chloroform and precipitated in cyclohexane, dialysis was effected to eliminate the non-reacted sodium azide. FT/IR and GPC analyses were carried out. FT/IR analysis revealed an absorption band at 2104 cm^-1 characteristic of the azide group. GPC (THF; 25°C) Mn 14000; PDI 1.15.

Example 13

Treatment with piperidine

Method (b) . Ϊ00 mg of PGMA in 2.5 mL of DMSO with 1.8 μΐ. of piperidine as first addition and 0.59 mL of piperidine as second addition. Heating to 80°C for 30 minutes. The mixture was dissolved in chloroform and precipitated in cyclohexane.

^■"^"H-NMR (400 MHz, CDC1₃) : 5_[DMSO-d6] : 0.76, 0.93, 1.6-2 (H chain) ; 1.36 (HI) ; 1.48 (H6) ; 2.27 (H4) ; 2.36 (H5) ; 3.6-4.0 (HI, H2); 4.7 (0H3) . GPC (DMF; 70°C) Mn 27700; PDI 1.04

Example 14

Treatment with 4-hydroxypiperidine

Polymer +

Method (b) . 100 mg of PGMA in 2.5 mL of DMSO with 1.18 mg of 4-hydroxypiperidine as first addition, and 0.61 g of 4-hydroxypiperidine as second addition. Heating to 80°C for 30 minutes. Dialysis was effected in water.

^-NMR (400 MHz, CDCI3) : <5_[DMSO-d6] : 0.76, 0.93 (H chain); 1.36, 1.68 (H5) ; 2.06, 2.28 {HA); 2.28, 2.70 (A3); 3.42 (H6) ; 3.48-4.1 (HI, H2); 4.55, 4.73 (OH7, OH8) . Example 15

Treatment with 3-hydroxypiperidine

Method (b) . 100 mg of PGMA in 2.5 mL of DMSO with 1.18 mg of 3-hydroxypiperidine as first addition, and 0.61 g of 3-hydroxypiperidine as second addition. Heating to 80°C for 30 minutes. Dialysis was effected in water. 1H-NMR (400 MHz, CDCI3) : 5_[DMSo-d6] : 0.78, 0.94, 1.95

(H chain) ; 1.4, 1.62 (JT7) ; 1.76, 1.83 (H6) ; 2.3 (H5, H8) ; 2.62, 2.80 (HA) ; 3.48 (H9) ; 3.6-4.0 (HI, H2) ; 4.6, 4.73 (OH3, OHIO) . Example 16

Treatment with N-methylpiperazine

Polymer +

Method (b) . 100 mg of PGMA in 2.5 mL of DMSO with 1.8 μΐί of N-methylpiperazine as first addition, and 0.67 mL of N-methylpiperazine as second addition. Heating to 80°C for 30 minutes. The mixture was dissolved in chloroform and precipitated in ethyl ether. H-NMR (400 MHz, CDCI₃) : 5_[Me0H-d4] : 0.95, 1.10, 1 2.15 (H chain) ; 2.38 (H6) ; 2.4-2.9 (H3, H4, H5) ; 3 4.15 (HI, H2) . Example 17

Treatment with methyl ethanolamine

Polymer +

Method (a) . 100 mg of PGMA in 2.5 mL of DMSO with 0.48 mL of methyl ethanolamine. The mixture was dissolved in chloroform and precipitated in ethyl ether.

^XH-NMR (400 MHz, CDCI3) : 5_[MeoH-d4] : 0.95, 1.11, 1.8- 2.2 (H chain) ; 2.4 (H4) ; 2.48-2.78 (A3, H5) ; 3.69 (H6) ; 3.8-4.25 (HI, H2) . GPC (DMF; 70°C) Mn 32000; PDI 1.04

Example 18

Treatment with diethanol amine

Polymer +

Method (b) . 100 mg of PGMA in 2.5 mL of DMSO, 1.8 L of diethanol amine, as_. first addition and 0.58 mL of diethanol amine as second addition. Dialysis was effected in water. Heating to 80°C for 1 hr. ¹H-NMR (400 MHz, CDC1₃) : O[DMS0-d6] · 0.78, 0.94, 1.6- 2.0 (H chain) ; 2.4-2.6 (H3) ; 2.58 (HA) ; 3.45 (HS) ; 3.73 (H2) ; 3.73, 3.90 (HI) ; 4.41 (0H7) ; 4.75 (OH6) . Example 19

Treatment with imidazole

Polymer +

Method (b) . 100 mg of PG A in 2.5 mL of DMSO, with 1.25 mg of imidazole as first addition and 0.41 g of imidazole as second addition. Heating to 80°C for 3 hr .

Example 20

Method (b) . 100 mg of PGMA in 2.5 mL of DMSO, with 2.17 mg of benzimidazole as first addition and 0.71 g of benzimidazole as second addition. Heating to 80°C for 16 hr.

Example 21

Treatment of the copolymer poly (glycidylmethacrylate) - jb-poly (methyl methacrylate) with morpholine.

TOO mg of the copolymer from example 4 were dissolved in 2.5 mL of DMSO, 0.52 mL of morpholine were added. The mixture was heated to 80°C for 2 hours. The volatile component was removed in a rotating evaporator at a pressure of about 1 Torr. Precipitation was effected by dripping a solution of the polymer in chloroform, into ethyl ether.

¹H-NMR (400 MHz, CDC1₃) , δ: 0.78-1.2, 1.7-2.1 ( H chain); 2.43 (HA) ; 2.58, 2.70 (H3) ; 3.60 (H6) ; 3.78 (H5) ; 3.84, 4.02 (HI); 4.02 (H2) .

Example 22

Treatment of the copolymer poly (glycidylmethacrylate) -

100 mg of the copolymer from example 5 were dissolved in 2.5 mL of DMSO, 0.52 mL of morpholine were added. The mixture was heated to.80 °C for 2 hours. The volatile component was removed in a rotating evaporator at a pressure of about 1 Torr. Precipitation was effected by dripping a solution of the polymer in chloroform, into ethyl ether. ¹H-NMR (400 MHz, CDC1₃), δ: 0.78-2.2 ( H chain); 2.45 (H4) ; 2.58, 2.70 (H3) ; 3.78 (HS) ; 3.84, 4.03 (HI); 4.03 (H2); 6.3- 6.7, 6.84-7.2 (HPh) .

Example 23

Treatment of the copolymer poly (glycidylmethacrylate) - jb-pol (butyl acrylate) with morpholine

100 mg of the copolymer from example 6 were dissolved in 2.5 mL of DMSO, 0.52 mL of morpholine were added. The mixture was heated to 80 °C for 2 hours. The volatile component was removed in a rotating evaporator at a pressure of about 1 Torr. Precipitation was effected by dripping a solution of the polymer in chloroform, into ethyl ether. ¹H-NMR (400 MHz, CDCI₃), δ: 0.92, ( CH2CH2CH2CH3 ) ; 1.09, 1.7-2.08, 2.18-2.40, (H chain); 1.38 ( CH2CH2CH2CH3 ) ; 1.60 ( CH2CH2CH2CH3 ) ; 2.48 (H4); 2.58, 2.70 (H3) ; 3.72 (H4) ; 3.9 ( OCH2CH2CH2CH3 ) ; 3.9-4.18 (H2, Hi) . Example 24

100 mg of PGMA were dissolved in DMSO, 50 μΐ, of triethyl amine and 0.1 mL of 2 mercaptoethanol were added. The mixture was heated to 80 °C for 2 hours. The volatile component was removed in a rotating evaporator at a pressure of about 1 Torr. Precipitation was effected by dripping a solution of the polymer in chloroform, into ethyl ether. NMR and GPC analyses were carried out. ¹H-NMR (400 MHz, CDC1₃) , δ: 0.78, 0.90, 1.6-2.1 (H chain); 2.60 (133, HA) ; 3.58 (H5) ; 3.64-4.20 (HI, H2) ; 4.78, 5.17 (OH6, OH7) . GPC (DMF; 70°C) Mn 57000; PDI 1.17

Example 25

100 mg of PGMA were dissolved in DMSO, 50 μΐ. of triethyl amine and 132 mg of phenol were added. The mixture was heated to 120 °C overnight. The volatile component was removed in a rotating evaporator at a pressure of about 1 Torr. Precipitation was effected by dripping a solution of the polymer in chloroform, into ethyl ether. NMR and GPC analyses were carried out. ¹H- NMR (400 MHz, CDC1₃) , <5: 0.8, 1.1, 1.5-2.15 (H chain); 3.65-4.25 (HI, H2, H3) ; 6,88 (H4, H6) ; 7.21 (235) . GPC is missing.

Example 26

Functionalization treatment of the hydroxyl group on polymers treated with nucleophiles

50 mg of polymer (from example 10) were dissolved in

2 mL of anhydrous chloroform in a nitrogen atmosphere, in a two-necked flask. 2 mL of a solution containing 77 μΐ· of phenyl isocyanate in anhydrous chloroform were added dropwise. At the end of the addition, the mixture was refluxed for 16 hours. The reaction was quenched by adding 10 mL of methanol. The volatile component was removed in a rotating evaporator at a pressure of about 1 Torr. Precipitation was effected by dripping a solution of the polymer in chloroform, into ethyl ether. ^XH-NMR (400 MHz, CDC1₃) , δ: 0.5- 1.3, 1.4-2 (H chain); 3.65-4.25 (HI, H2, H3) ; 6,88 (HA, H6) ; 7.21 (H5) . GPC (THF; 25°C) Mn 20000; PDI 1.20

Example 27

Formation of hydrogel (hyper-crosslinking)

50 mg of polymer treated with morpholine (from example 8) were dissolved in 3 mL of deionized water, and the solution was placed in a dialysis tube. The dialysis tube was immersed in a flask containing 2 L of deionized water, which was heated to 60°C for 16 hours. The solution containing the polymer inside the dialysis tube was then lyophilized. NMR and DLS analyses were carried out. The appearance of the peak 5.48 ppm upon NMR analysis [corresponding to hydrogen (CO) OCH₂CH(CH₂N) 0 (CO) -] reveals the formation of interchain ester bridges. The N indicated in the above formula is part of the morpholine.

Example 28

Formation of hydrogel (hyper-crosslinking) in an acid environment

50 mg of polymer treated with morpholine (from example 8) were dissolved in 3 mL of deionized water, and the solution was placed in a dialysis tube. The dialysis tube was immersed in a flask containing 2 L of a solution of HC1 0.05 M, which was heated to 60°C for 16 hours. The dialysis tube was then placed in a flask containing 2 L of a solution of NaHC0₃ 0.01 M, and finally in deionized water. The solution containing the polymer inside the dialysis tube was then lyophilized. NMR and DLS analyses were carried out. The appearance of the peak 5.48 ppm upon NMR analysis [corresponding to hydrogen - (CO) OCH₂Cff(CH₂N) 0 (CO) -] reveals the formation of inter-chain ester bridges. The N indicated in the above formula is part of the morpholine.

Claims

1. A process for the treatment of a polymer containing at least one group having formula I :

wherein the carbon of the carboxyl function is connected to the remaining part of the polymer;

the process comprises a first reaction phase, during which the polymer reacts with a nucleophile (H- Nu, Nu^") in the presence of an organic solvent so that the group having formula I is modified so as to have formula II:

the organic solvent is aprotic, it has a dipole moment greater than 0 and at least one oxygen atom, which, in particular, is capable of effectively binding itself by means of a hydrogen bridge;

the nucleophile being selected from the group consisting of: secondary amines, thiols and aromatic alcohols, wherein a hydroxyl group is directly bound to an aromatic ring, and anionic reagents such as azides and thiocyanates .

2. The process according to claim 1, wherein the organic solvent has a dipole moment greater than 3.5.

3. The process according to claim 1, wherein the organic solvent is selected from the group consisting of: DMSO (dimethylsulfoxide) , Dimethylformamide, Dimethylacetamide, Dioxane, THF ( tetrahydrofuran) , Acetone, Ethyl acetate, Methyl acetate, 1 , 3-Dimethyl-2- imidazolidinone, Nitromethane, Nitroethane, Sulfolane, N-Methylpyrrolidone, Propylene carbonate,

Hexamethylphosphorictriamide, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, Nitrobenzene .

4. The process according to claim 1, wherein the organic solvent is selected from the group consisting of: DMSO, Dimethylformamide, Dimethylacetamide, 1,3- Dimethyl-2-imidazolidinone, Nitromethane, Nitroethane, Sulfolane, N-Methylpyrrolidone, Propylene carbonate, Hexamethylphosphorictriamide .

5. The process according to claim 4, wherein the organic solvent is selected from the group consisting of: DMSO, Dimethylformamide, Dimethylacetamide, 1,3- Dimethyl-2-imidazolidinone, Sulfolane, N-Methylpyrrolidone, Propylene carbonate, Hexamethylphosphorictriamide; in particular, the organic solvent is DMSO.

6. The process according to any of the previous ^■claims, wherein the nucleophile is selected from the group consisting of: secondary amines, thiols and aromatic alcohols, wherein a hydroxyl group is bound directly to an aromatic group.

7. The process according to any of the previous claims, wherein the secondary amine is not of the group consisting of:

8. The process according to any of the previous claims, wherein the secondary amines are C2-C14; the thiols are C1-C10; the aromatic alcohols are C4-C26 alcohols of an aromatic group, in particular, selected from the group consisting of: pyridine, pyrrole, furane, thiophene, imidazole, pyrimidine, quinoline, isoquinoline, indole, purine, benzene naphthalene, anthracene, phenanthrene, pyrene, benzopyrene .

9. The process according to claim 8, wherein the secondary amines are C2-C₈ and have formula HNR^XR² (III) wherein R¹ and R² are each independently selected from the group consisting of: C1-C7 alkyl, C2-C7 alkenyl having from 1 to 3 double bonds; optionally, R¹ comprises from 1 to 2 oxygen atoms, each of which is ether or hydroxyl, and from 1 to 3 nitrogen atoms, each independently, tertiary or secondary; optionally, R² comprises from 1 to 2 oxygen atoms, each of which is ether or hydroxyl, and from 1 to 3 nitrogen atoms, each independently, tertiary or secondary; optionally, R¹ and R² are bound to each other so as to form from 1 to 3 cycles ;

the thiols are Ci-Cs alkyls having at least one SH functionality and optionally have from 1 to 2 hydroxy functionalities ;

the aromatic alcohols are alcohols of compounds selected from the group consisting of: furane, thiophene, benzene, naphthalene, anthracene, phenanthrene , pyrene, benzopyrene, triphenylene, coronene, hexahelicene .

10. The process according to any of the previous claims, wherein the polymer comprises at least one poly (glycidyl methacrylate ) (PGMA) chain, in particular obtained by means of RAFT Reversible Addition- Fragmentation chain Transfer) ; the group with formula I having formula la:

11. The process according to any of the previous claims, comprising an addition phase, which follows the first reaction phase and during which a compound selected from the group consisting of isocyanate R-NCO, X-Y and K-Z, is added to the hydroxyl of the group having formula II; X is selected from the group consisting of CI, Br; Y is selected from the group consisting of: -COR, -C(0)OR, -P(0) (OR)₂, -S(0)₂OR; K and Z each indicate -OC(0)R; R indicates a substituent, in particular Ci-Cio, selected from the group consisting of: aliphatic groups optionally substituted, aromatic groups optionally substituted and a combination thereof;

when the addition phase is effected with isocyanate, the group having formula II is modified so as to have formula IV:

when the addition phase is effected with K-Z, the group having formula II is modified so as to have formula VI :

12. The process according to claim 11, wherein the addition is effected with isocyanate.

13. The process according to any of the previous claims, wherein the polymer also comprises at least one additional group having formula I; the. process comprising a second reaction phase, during which an anionic reagent (A) reacts with an additional group having formula (I) so as to obtain the group having formula VII:

14. The process according to claim 13, wherein the anionic reagent is selected from the group consisting of: azides, thiocyanates ; the second reaction phase following the first reaction phase.

15. The process according to any of the previous claims, comprising a crosslinking phase, which at least partially follows the first reaction phase and during which two groups having formula II:

react with each other so as to obtain the formation ester bridges having formula VIII:

16. A polymer having at least one group having the formula according to any of the previous claims and selected from the group consisting of: formula II formula IV, formula V, formula VI, formula VII, formul VIII.