EP2064255A1 - Process for preparing a triblock copolymer comprising a semi-crystalline and/or hydrolysable block, an elastomeric block and an amorphous block - Google Patents

Abstract

The invention relates to a process for preparing a block copolymer comprising a sequence comprising successively a semi-crystalline and/or hydrolysable block, an elastomeric block and an amorphous block, said process comprising the following steps: a) a step of 1,2-addition, on an ethylenic end group of a semi-crystalline and/or hydrolysable polymer, of an alkoxy amine that may correspond to the following formula (II): b) a step of addition, to the medium derived from step a), of one or more monomers that are precursors of the elastomeric block, as a result of which a semi-crystalline block-b-elastomeric block diblock copolymer is obtained; c) a step of addition, to the medium derived from step b), of one or more monomers that are precursors of the amorphous block, as a result of which the semi-crystalline and/or hydrolysable block-b-elastomeric block-b-amorphous block triblock copolymer is obtained. Use of the copolymers obtained as amorphous matrix impact modifier.

Description

 PROCESS FOR PREPARING A TRIBLOC COPOLYMER

COMPRISING A SEMI-CRYSTALLINE AND / OR HYDROLYSABLE BLOCK,

AN ELASTOMERIC BLOCK AND AN AMORPHOUS BLOCK

DESCRIPTION

TECHNICAL AREA

The invention relates to a process for the preparation of a triblock copolymer, comprising a semi-crystalline and / or hydrolysable block, an elastomeric block and an amorphous block by controlled radical polymerization using a particular alkoxyamine.

These triblock copolymers thus prepared can find particular application in areas requiring the use of materials with very high mechanical tensile strength and can be used in particular as impact modifier of a fragile amorphous polymer matrix.

When one of the blocks is hydrolysable, these copolymers can find their application in the formation of nanoporous films or as an anti-fouling paint ingredient.

STATE OF THE PRIOR ART

Block copolymers comprising a semicrystalline block, an elastomeric block and an amorphous block have been essentially prepared so far by ionic polymerization, such as anionic polymerization or cationic polymerization. Thus, Balsamo et al. (Macromolecular Chemistry and Physics 1996, 197, 1159-1169) have described the preparation of a polystyrene-β-polybutadiene-β-poly (ε-caprolactone) triblock copolymer by successive anionic polymerization of styrene, butadiene and finally ε- caprolactone after end-chain modification of the polystyrene-polybutadiene diblock copolymer with diphenylethylene.

Abetz et al. (Macromolecules 2001, 34, 8720-8729) have described the synthesis of a polystyrene-b-poly (ethylene-alt-propylene) -b-polyethylene block copolymer (PS-fc-PEP-fc-PE), where PE represents the semi-crystalline block, PS represents the amorphous block and PEP represents the elastomer block, this synthesis being carried out by sequential anionic polymerization of styrene, isoprene and 1,4-butadiene, followed by partial hydrogenation of the polyisoprene blocks and polybutadiene, to yield the aforementioned triblock copolymer. Faust and Kwon (Journal of Macromolecular

Science, Part A: Pure and Applied Chemistry 2004, 42, 385-401) have described the synthesis of a poly (α-methylstyrene) -b-polyisobutylene-β-polypivalactone block copolymer, where the amorphous character is conferred by the poly (α-methylstyrene), the elastomeric character is conferred by the polyisobutylene and the semi-crystalline character is conferred by the polypivalactone, this synthesis being carried out by successive cationic polymerizations of α-methylstyrene and isobutylene, followed by the polymerization anionic effect of pivalactone following a chemical modification in end of the poly (α-methylstyrene) -b-polyisobutylene diblock copolymer.

Bats et al. (Macromolecules 2001, 34, 6994-7008) have described the synthesis of a polystyrene-β-polyisoprene-β-polyethylene triblock triblock copolymer from a block process combining the anionic polymerization of styrene, isoprene and ethylene oxide.

Hillmyer (Chemical Materials 2006, 18, 1719-1721) has described, in particular, poly (lactic acid) -bim-polyisoprene-β-polystyrene block copolymers comprising a polyisoprene elastomer block, an amorphous polystyrene block and a biodegradable poly (lactic acid) block. these copolymers being synthesized by anionic polymerization of styrene, isoprene and by coordination-insertion polymerization of lactic acid in the presence of triethylaluminium.

These various processes, based on ionic polymerization (cationic and / or anionic) have a certain number of disadvantages, in that they are very sensitive to traces of impurities in solvents and in particular traces of water. Moreover, they do not provide control of the polymerization reactions of a wide range of monomers.

Some authors have described the use of the controlled radical polymerization technique by using, as macroinitiator, an end-activated polycaprolactone, called TEMPO, of formula:

the hook indicating the location by which the TEMPO end is attached to the polycaprolactone.

This activated polycaprolactone, called PCL-TEMPO, is used as a living polymer to polymerize styrene, to form a polycaprolactone-fc-polystyrene diblock copolymer. Considering the synthesis of a polycaprolactone-poly (n-butyl acrylate) diblock copolymer is constraining from PCL-TEMPO, since the polymerization control of n-butyl acrylate by nitroxide TEMPO can only be assured by controlled addition of ascorbic acid in the reaction medium. In the document Macromolecules, 1999, 32,

8356-8362, there is described the preparation of a poly (butadiene) -b-poly (styrene) diblock copolymer comprising the following steps: a) an anionic polymerization step of butadiene with sec-butyllithium; b) a reaction step of polybutadienyl-Li with an alkoxyamine of the following formula:

at the end of which we obtain the following living polymer:

c) a step of living radical polymerization of the living polymer obtained previously with styrene, after which the following polymer is obtained:

This document does not disclose a copolymer preparation comprising a semi-crystalline and / or hydrolysable block, an elastomeric block and an amorphous block.

Documents FR 2789991, WO 00/71501, EP 1526138 and FR 2866026 describe water-soluble alkoxyamines and processes for preparing (co) polymers from these water-soluble alkoxyamines. However, it is neither disclosed nor suggested in these documents the preparation of copolymers comprising a semi-crystalline block and / or hydrolyzable, an elastomeric block and an amorphous block.

There is therefore a real need for a process for preparing a triblock copolymer (block semi-crystalline and / or hydrolysable) -b- (elastomeric block) -b- (amorphous block) allowing polymerization control of each of the blocks and, moreover, not requiring operating conditions as exacting as the ionic polymerization or else radical polymerization with an initiator of the TEMPO type as defined above.

This need is filled by the invention object of the description below.

STATEMENT OF THE INVENTION

The invention thus relates, according to a first object, to a process for preparing a triblock copolymer comprising a semi-crystalline and / or hydrolysable block, an elastomeric block and an amorphous block, comprising the following steps: a) a a 1,2-addition step on an ethylenic terminal group of a semi-crystalline and / or hydrolysable polymer of an alkoxyamine corresponding to the following formula (I):

R ₁ C (CH ₃ ) ₃

R ₃ -CON CH-C (CH ₃ ) ₃ C (O) OR ₂ P (O) (OEt) ₂

(D in which:

R 1 and R ₃ , which may be identical or different, represent a linear or branched alkyl group having a number of carbon atoms ranging from 1 to 3;

R ₂ represents a hydrogen atom, an alkali metal, such as Li, Na, K, an ammonium ion such as NH ₄ ⁺ , NBu ₄ ⁺ , NHBu ₃ ⁺ , an alkyl group, linear or branched, having a number of carbon atoms ranging from 1 to 8, a phenyl group; b) a step of bringing into contact with the medium resulting from step a) of one or more precursor monomers of the elastomer block for a time sufficient to obtain a semicrystalline block copolymer and / or a hydrolyzable block-block copolymer elastomer ; c) a step of contacting with the medium resulting from step b) of one or more precursor monomers of the amorphous block, for a sufficient time to obtain the triblock block copolymer semi-crystalline and / or hydrolyzable-jb-block amorphous elastomer-jb-block.

Before going into more detail in the description, it is specified that by precursor monomer of the elastomer block and amorphous block precursor monomer is meant the monomers which, after polymerization, will respectively constitute the repeating units of the elastomeric block and the amorphous block.

It is specified that Et denotes an ethyl group and Bu, a butyl group, which can exist under its different isomers.

The innovative nature of this process lies particularly in: the 1,2 addition of the alkoxyamine to an ethylenic group of a semi-crystalline and / or hydrolyzable polymer intended to constitute the semicrystalline and / or hydrolysable block;

the controlled radical polymerization recovery from the semi-crystalline and / or hydrolysable polymer activated by a group derived from Alkoxyamine, this resumption of polymerization to obtain the elastomeric block covalently attached to the semi-crystalline block and / or hydrolysable; the controlled radical polymerization recovery from the semicrystalline block copolymer and / or hydrolysable-elastomer block copolymer, one end of the elastomeric block of which is activated by a group derived from the alkoxyamine; the controlled nature of the polymerization steps.

A reaction scheme will be explained above starting from a specific example.

In step a) of the process, a semi-crystalline and / or hydrolysable polymer is brought into contact with an alkoxyamine of formula (I), this alkoxyamine being capable of reacting with the ethylenic group of the polymer according to an addition reaction. 2.

The semi-crystalline and / or hydrolysable polymer may be: a non-hydrolyzable semi-crystalline polymer, such as polyethylene, polypropylene, polyethylene oxide and polyamides;

a hydrolyzable semi-crystalline polymer, such as the polymers resulting from a polycondensation reaction, such as polycaprolactones, L-polylactide and poly (L-lactide-co-glycolic acid) copolymers; a hydrolyzable non-semicrystalline polymer, such as DL-polylactide and poly (DL-lactide-co-glycolic acid) copolymers.

In the remainder of this disclosure, polylactide is understood to mean poly-L-lactides and poly-DL-lactides.

These polymers can be prepared beforehand or can be purchased from appropriate suppliers. It is specified that hydrolysable polymer means a polymer capable of being cleaved into these repeating units by hydrolysis in an aqueous medium, this hydrolysis can be carried out in an acidic or basic medium depending on the nature of the polymer.

The method according to the invention may comprise a step prior to step a), said functionalization step, intended to introduce at the end of a semicrystalline and / or hydrolyzable starting polymer, an ethylenic terminal group, when the latter is not inherently part of this polymer.

For example, starting from a semi-crystalline starting polymer having an -OH end, such as a ca-hydroxylated polycaprolactone, it is necessary to react the latter with a compound capable of introducing an ethylenic group by reaction with the -OH end. This compound may be chosen from acids, activated esters, acryloyl halides, such as acryloyl chloride, to which case the ethylenic group introduced is an acrylate group.

The reaction scheme, with acryloyl chloride as compound, can be as follows:

Polymer-OH + Cl

According to the invention, the semi-crystalline and / or hydrolysable polymer comprising an ethylenic group (intended to constitute the semicrystalline and / or hydrolysable block) is brought into contact with an alkoxyamine as defined above and reacts with it. according to an addition mechanism 1,2 according to the following reaction scheme:

the nitroxide end being hereinafter referred to as "SGl".

The alkoxyamine is generally introduced in a content ranging from 0.5% to 80% by weight relative to the weight of the semi-crystalline and / or hydrolysable polymer, whose number-average molar mass Mn can be in the range from 1000 g. mol ^"1 to 100 000g. ^{mol" 1} and, preferably, 5000 g. mol ^"1 to 50,000 g mol ^-1 .

A particular alkoxyamine which can be used in accordance with the invention is an alkoxyamine corresponding to the following formula (II):

(H) which can be called, in the rest of this presentation,

"MAMA-SGl".

The semi-crystalline and / or hydrolysable polymer activated by an SGl end constitutes a living polymer, which will be able to serve as a basis for the controlled synthesis of the second block by polymerization of one or more precursor monomers of the elastomeric block.

The monomers introduced in step b) precursors of the elastomer block may be chosen from alkyl acrylates such as n-acrylate and butyl and dienes, such as isoprene and butadiene.

It may be advantageous to generate the resumption of polymerization from the semi-crystalline and / or hydrolyzable living polymer obtained at the end of step a), to add, during step b) in addition to the monomers intended to form the elastomeric block, a solution comprising a control agent corresponding to the following formula:

and a solvent for this control agent, which solvent may be tert-butylbenzene (t-BuBz) or chlorobenzene, which solvent does not participate in the transfer reactions.

At the end of step b), a diblock copolymer (semi-crystalline block and / or hydrolyzable block) -beta-elastomer block activated at the end of the elastomer block is thus obtained by a group of formula:

the hook indicating the location by which this group is attached to the end of the elastomeric block.

With this activated end, the diblock copolymer (semicrystalline block and / or hydrolysable) -jb-elastomer block will be able to serve as a basis for the controlled synthesis of the third block by polymerization of one or more precursor monomers of the amorphous block.

The monomers introduced in step c) precursors of the amorphous block may be chosen from alkyl methacrylates such as methyl methacrylate, styrene, acrylic acid, alkyl methacrylamides and vinyl acetate.

Steps a), b) and c) are generally carried out in an inert gas atmosphere, for example, nitrogen, for example by sparging nitrogen into the reaction system.

Steps a), b) and c) are also carried out at a temperature ranging from 20 ^° C. to 180 ^° C., preferably from 40 ° C. to 130 ^° C.

The method of the invention may comprise, after steps a), b) and c), a step of isolating the living polymer, at the end of step a), a step of isolating the diblock copolymer of step b) and the triblock copolymer of step c), for example by precipitation followed by filtration. The process of the invention is particularly applicable to the preparation of a triblock copolymer, wherein: the semi-crystalline block is a polycaprolactone block; the elastomer block is a poly (n-butyl acrylate) block; the amorphous block is a poly (methyl methacrylate) block. From a structural point of view, the process according to the invention makes it possible to obtain triblock copolymers (semi-crystalline and / or hydrolysable block) -b- (elastomeric block) -b- (amorphous block) having a bound terminal group to the amorphous block having the following formula:

Thus, the invention relates, according to a second object, to a triblock copolymer obtainable by the process of the invention.

These triblock copolymers, because of a sequence comprising a semicrystalline and / or hydrolysable block, an elastomer block and an amorphous block, make it possible for them to have a high potential as impact modifier of fragile polymeric matrices (for example, in amorphous polymer, thermosetting or semi-crystalline), the triblock copolymer can be introduced in a content of 25 to 50% by weight relative to the mass of the matrix. Indeed, these triblock copolymers can self-assemble in the form of core-corona nanoparticles, with a semi-crystalline core, an elastomer ring, to diffuse the stress experienced by the copolymer and an amorphous polymer crown. In the case of an amorphous polymer matrix, the amorphous ring allows compatibility between the nanoparticles and the amorphous matrix to be modified.

The triblock copolymer according to the invention may be used to increase the impact and / or impact resistance properties and / or the strength properties of a polymeric matrix, which may be amorphous, thermosetting or semi-crystalline. According to a particular embodiment of the invention, the polymeric matrix is amorphous polymer. The polymeric matrix can be made of epoxy, unsaturated polyester, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polyphenylene oxide, polymethyl methacrylate, polyvinylidene fluoride, polycarbonate.

In particular, a triblock copolymer according to the invention comprising an amorphous polystyrene or polymethylmethacrylate block can serve as an impact modifier to a polystyrene, polyethylene oxide, polymethyl methacrylate, polyvinylidene fluoride or polycarbonate matrix. Thus, the invention relates to a composite material comprising an amorphous polymer matrix, thermosetting or semi-crystalline, for example amorphous polymer such as polymethyl methacrylate, and a triblock copolymer as defined above.

When the first block is hydrolysable, in addition possibly to be semi-crystalline, it may also be possible to use the capacity of this block to cavitate in many applications, involving the formation of pores generated by the hydrolysis of this material. block.

Thus, it may be conceivable to use these copolymers in the formation of nanoporous films, the hydrolysis of the hydrolysable core possibly making it possible to form pores in a film containing nanoparticles.

Finally, it may be possible to use these copolymers as an ingredient in the field of antifouling paint, particularly in the field of navigation. In a schematic way, the nanostructuration in the form of cylinders of these copolymers would allow, after degradation of the hydrolyzable block, the structuring of the "niche" paint layer making the superhydrophobic protected surface and thus preventing the water but also the microorganisms that it contains to be deposited on the walls of the boat. The invention will now be described with reference to the following examples given for illustrative and non-limiting.

DETAILED PRESENTATION OF PARTICULAR EMBODIMENTS

EXAMPLE

a) Obtaining polycaprolactone acrylate

In a three-necked flask, a ω-hydroxylated polycaprolactone is dissolved in dichloromethane ([OH] = 10 ^-2 mol.l ^-1 ) Finally, 25 equivalents of acryloyl chloride are added using a syringe. The mixture is allowed to stir for a weekend at ambient temperature and under an inert atmosphere (reaction time greater than 60 hours), the dichloromethane is then evaporated in vacuo and the polymer is in the form of an oil. in tetrahydrofuran (THF), the polycaprolactone having an acrylate group at its end is precipitated in cold methanol, filtered on a frit, rinsed with methanol and finally dried on a vacuum ramp for a few hours. white powder The functionalization yield, determined by ¹ H NMR, is 100% according to this method of synthesis The reaction time can be optimized by increasing the number of equivalents of chloride of acryloyl or by increasing the concentration of the polymer in the medium. Thus, using 100 equivalents of acryloyl chloride, it was possible to achieve a functionalization efficiency of 100% in 20 hours. Similarly, the reaction is complete in 20 hours, when the concentration of the OH function is increased to 2.5 * 10 ^{~ 2} mol. L ^"1 , after decreasing the amount of solvent used in the reaction.

The polymer obtained has the following formula (III):

(III)

n corresponding to the number of repeating units, namely 88.

The NMR analysis results are as follows:

¹ H NMR (CDCl ₃₎ (ppm): 6.4 (dd, J _a - _b = 17.4 Hz, _J _ _a - = 1.4 Hz); 6.1-6.2 (m); 5,8- 5,9 (dd, J ^_a, _ _b = 10.7, J ^_a, _ _a = l, 2 Hz), 4.1 (t, J _5-4 = 6, 65 Hz, 2H) ; 2.3 (t, J - ₂ = 7,45Hz, _2H!); 1.7 (m, 4H); 1.4 (m, 2H).

b) 1,2-Addition of MAMA-SG1 by Polycaprolactone Acrylate

The polycaprolactone having an acrylate end group of formula (III) is introduced into a Schlenk tube equipped with a rotaflo tap. A solution of MAMA-SG1 of formula (II) below:

(H)

in THF is introduced on the polycaprolactone of formula (III) (optimum concentration of the acrylate function 0.05 mol.l ^-1 ) The suspension of polycaprolactone (III) in THF containing the MAMA-SGl is deoxygenated by bubbling d Finally, the Schlenk tube is immersed in an oil bath at 100 ^° C. for 1 hour The medium is rapidly homogenized at 100 ^° C. (the dissolution of the polymer being favored by its melting). Once the Schlenk tube has cooled down, the reaction medium is transferred to a monocolumn flask with the THF used to rinse off said Schlenk tube.The medium is slightly reconcentrated by evaporation under vacuum at a maximum temperature of 30 ^° C. so as not to damage the The polymer end is then precipitated in cold methanol, filtered and rinsed with methanol Finally, the polymer, corresponding to a white powder, is dried on a vacuum ramp.

This polymer has the following formula:

In the rest of the example, this polymer is called PCL-SG1.

Its living character (100%) is determined by NMR 3I ₁ P and RPE according to the works published in the following articles: Bertin et al., E-Polymers, 2003, n ° 2; Bertin et al., Macromolecules, 2002, 35, 3790-3791.

The NMR analysis results are as follows:

¹ H NMR (CDCl ₃ ) (in ppm): 4.0 (t, J ₅ - ₄ = 6.15 Hz, 2H); 2.3 (t, Ji ₂ = 7.1 Hz, 2H); 1.6 (m, 4H), 1.1 (m, 2H); 1.4 (s, H _b ); 1.4 (s, H _a )

³¹ P NMR (CDCl ₃ ) (in ppm): a peak at 24.43 ppm (majority diastereoisomer, 85%) and a peak at 24.15 ppm (minority diastereoisomer, 15%). c) Polymerization of n-butyl acrylate initiated by PCL-SG1

The PCL-SG1 macroinitiator is introduced into a three-necked flask containing n-butyl acrylate. Tert-butylbenzene (t-BuBz) and a solution of SG1 in t-Bubz corresponding to 10 mol% of SGl relative to the macroinitiator are added to the three-necked flask. The reaction system is deoxygenated by bubbling nitrogen for 20 minutes and is then heated to 120 ^° C. (temperature ramp in 20 minutes). The reaction is stopped by stopping the heating after 2:30 of reaction by immersing the flask in an ice-water bath. The medium is re-concentrated to maximum vacuum and then precipitated directly in cold methanol. A precipitate of a diblock copolymer PCL-b-PBA is thus obtained. The copolymer is then filtered, rinsed with methanol and dried on a vacuum ramp. The appearance of a diblock copolymer with M _n (PCL) = 10,000 g. mol -1 and

M _n (PBA) = 20,000 g. mol -1 corresponds to a sticky solid and slightly translucent.

The copolymer obtained corresponds to the following formula

This copolymer is hereinafter referred to as PCL - & - PBA-SG1.

This stage is perfectly controlled and alive, insofar as:

In (Mo / M) is linear as a function of time (t) (M ₀ being the molar mass of the copolymer to T and M the molar mass of the copolymer at time t); the M _n evolves linearly and increasingly with the conversion; the Ip (polydispersity index) of the PCL-b-PBA-SGl copolymers is equal to that of the commercial PCL used as starting material, which means that there is no increase in I _p ;

the% of SG1 at the end of the chain (ie, in other words, the level of living chains) of the copolymers exceeds 85%.

The NMR results are as follows:

¹ H NMR (CDCl ₃ ) (in ppm):

4.1 (m, H ₅ , H ₈ ); 2.3 (t, H ₁ , H ₇ ); 1.6 (m, 4H), 1.8 and 1.6

(m, H ₂ , H ₄ , H ₆ and H ₉ ); 1.4 (m, H ₃ , H ₁₀ ); 0.93 (t, H ₁₁ ).

³¹ P NMR (CDCl ₃ ) (in ppm): a solid mass at 24.7 ppm and a solid mass at 24.23 ppm. d) Polymerization of methyl methacrylate by the PCL-fc-PBA-SGl copolymer

The PCL-β-PBA-SGl copolymer, methyl methacrylate (target theoretical molecular weight of 450,000 g mol ^-1 ) and t-BuB 2 are introduced into a three-necked flask. The reaction system is deoxygenated by bubbling with nitrogen for 20 minutes and is then heated to 100 ^° C. (temperature ramp in 15 minutes). The reaction is stopped after 1 hour of reaction. The medium is diluted in THF and then precipitated in cold methanol. The polymer obtained is filtered on frit, rinsed with methanol and dried on a vacuum ramp. The terpolymer obtained is in the form of a white filamentous solid.

n, x and y corresponding to the number of repetitive units in parentheses.

The NMR results are as follows: ¹ H NMR (CDCl ₃ ) (in ppm): 4.1 (m, H ₅ , H ₈ ); 3.6 (m, H ₁₂ ); 2.3 (t, H ₁ , H ₇ ), 1.6 (m, 4H); 1.8 and 1.6 (m, H ₂ , H ₄ , H ₆ , H ₉ and H ₁₄ ), 1.4 (m, H ₃ , H ₁₀ ); 0.9-1.04 (t, H ₁₁ and H ₁₃ ). The table below describes three samples obtained according to the process described above:

PCL corresponding to the polycaprolactone block,

- PBA corresponding to the block poly (n-butyl acrylate);

PMMA corresponding to poly (methyl methacrylate) block;

Ip corresponding to the polydispersity index.

By reading this table, it can be seen that the process of the invention has a controlled nature and does not give rise to an increase in the polydispersity index starting from a polycaprolactone having an Ip of 1.7.

The copolymers prepared below have a high efficiency in improving the strength of polymethylmethacrylate.

Claims

A process for preparing a triblock copolymer comprising a semi-crystalline and / or hydrolyzable block, an elastomeric block and an amorphous block, comprising the steps of: a) a 1,2-addition step on an ethylenic terminal group a semi-crystalline and / or hydrolysable polymer of an alkoxyamine corresponding to the following formula (I): R ₁ C (CH ₃ ) ₃ R ₃ -CON CH-C (CH ₃ ) _{3 I0} C (O) OR ₂ P (O) (OEt) ₂ (D in which: R 1 and R 3, which may be identical or different, represent a linear or branched alkyl group, Having a number of carbon atoms ranging from 1 to 3; R ₂ represents a hydrogen atom, an alkali metal, such as Li, Na, K, an ammonium ion such as NH ₄ ⁺ , NBu ₄ ⁺ , NHBu 3 ⁺ , a linear or branched alkyl group having a number of carbon atoms ranging from 1-8, phenyl; b) a step of bringing into contact with the medium resulting from step a) of one or more precursor monomers of the elastomeric block for a time sufficient to obtain a semi-block diblock copolymer; Crystalline and / or hydrolyzable-elastomeric block; c) a step of bringing into contact with the medium resulting from step b) of one or more precursor monomers of the amorphous block, for a sufficient time to obtain the triblock block copolymer semi-crystalline and / or hydrolyzable-jb-block elastomer-jb-amorphous block. 2. The process as claimed in claim 1, in which the semicrystalline and / or hydrolyzable polymer comprising an ethylenic end group is chosen from polycaprolactones, polylactides, polyethylene, polypropylene, polyethylene oxide and polyamides. 3. Method according to claim 1 or 2, further comprising, prior to step a), a step of functionalizing the semicrystalline and / or hydrolysable polymer, said semicrystalline and / or hydrolyzable starting polymer intended for introduce the ethylenic terminal group. 4. The method of claim 3, wherein the semicrystalline polymer and / or hydrolyzable starting material is a ca-hydroxylated polycaprolactone. The process according to any one of the preceding claims, wherein the alkoxyamine used in step (a) has the following formula (II): (H) 6. Method according to any one of the preceding claims, wherein the alkoxyamine is introduced, in step a), in a content ranging from 0.5% to 80% by weight relative to the weight of the semi-crystalline polymer. and / or hydrolysable. 7. Method according to any preceding claim, wherein the monomers introduced in step b) precursors of the elastomeric block are selected from alkyl acrylates, dienes. 8. Process according to any one of the preceding claims, comprising adding, during step b) in addition to the monomers intended to constitute the elastomeric block, a solution comprising a control agent corresponding to the following formula : and a solvent for this control agent. 9. Process according to any one of the preceding claims, in which the monomers introduced in stage c) precursors of the amorphous block are chosen from alkyl methacrylates, styrene, acrylic acid and alkyl methacrylamides. vinyl acetate. 10. Process according to any one of the preceding claims, in which the semicrystalline and / or hydrolyzable block is a polycaprolactone block, the elastomer block is a poly (n-butyl acrylate) block, the amorphous block is a poly block. (methyl methacrylate). 11. A triblock copolymer obtainable by a process as defined in any one of claims 1 to 10. 12. Use of a copolymer as defined in claim 11, as impact modifier of an amorphous polymer matrix, thermosetting or semi-crystalline. Composite material comprising an amorphous, thermosetting or semi-crystalline polymer matrix and a triblock copolymer as defined in claim 11. 14. Composite material according to claim 13, wherein the matrix, when made of amorphous polymer, is polymethyl methacrylate. 15. Use of a copolymer as defined in claim 11 for the formation of nanoporous films. 16. Use of a copolymer as defined in claim 11 as an ingredient of an antifouling paint. 17. Use of a copolymer as defined in claim 11 to increase the impact properties and / or impact resistance and / or the strength properties of a polymeric matrix.