Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
  • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
  • C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
  • C08G63/08—Lactones or lactides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/91—Polymers modified by chemical after-treatment
  • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2230/00—Compositions for preparing biodegradable polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

Definitions

• the present invention relates to the field of nanostructured block copolymers having nano-domains oriented in a particular direction.
• the invention relates to a block copolymer film comprising at least one amorphous block, capable of being easily removed after structuring, and having a high phase segregation, with a low Lo period, preferably less at 20nm.
• noted Lo means the minimum distance separating two neighboring domains of the same chemical composition, separated by a different chemical composition area.
• block copolymers it is possible to structure the arrangement of the constituent blocks of the copolymers, by phase segregation between the blocks thus forming nano-domains, at scales of less than 50 nm. Because of this ability to nanostructure, the use of block copolymers in the fields of electronics or optoelectronics is now well known.
• the nano-domains must be oriented perpendicular to the surface of the underlying layer.
• Such a structuring of the domains requires particular conditions such as the preparation of the surface of the underlying layer, but also the composition of the block copolymer.
• An important factor is the phase segregation factor, also referred to as the Flory-Huggins interaction parameter and denoted " ⁇ ".
• This parameter makes it possible to control the size of the nano domains. More particularly, it defines the tendency of blocks of the block copolymer to separate into nano-domains.
• the product ⁇ , the Flory-Huggins parameter ⁇ and the degree of polymerization N give an indication of the compatibility of two blocks and whether they can separate at a given temperature. For example, a diblock copolymer of strictly symmetrical composition separates into micro-domains if the product ⁇ is greater than 10.49. If this product ⁇ is less than 10.49, the blocks mix and the phase separation is not observed at the observation temperature.
• PLA poly lactic acid
• PCL polycaprolactone
• PS polystyrene
• PDMS polydimethylsiloxane
• PTMSS polytrimethylsilylstyrene
• the Applicant has been particularly interested in polyesters polylactones type.
• the ring-opening polymerization of lactones has been studied for some years because the resulting polymers have a certain industrial interest in various fields because of their biodegradability and biocompatibility.
• copolymers with biodegradable polyesters can be used as a drug encapsulant or as biodegradable implants, particularly in orthopedics, to suppress the interventions that were necessary in the past to remove metal parts such as pins for example.
• Such polymers can also be used in coating and plastic formulations.
• Organo-catalysts have been developed to allow the ring opening polymerization of lactones, in particular ⁇ -caprolactone noted “ ⁇ -CL” in the following description.
• AMS methanesulfonic acid
• AMS in combination with a protic initiator of alcohol type, AMS is capable of promoting the controlled polymerization of the cyclic monomer ⁇ -caprolactone.
• the protic initiator allows fine control of average molar masses as well as chain ends.
• T g or T m melting high it may be necessary to perform annealing at a high annealing temperature to to promote nanostructuring. If the annealing treatment is to be carried out at a high temperature, typically above 200 ° C, and with slow segregation kinetics, this can lead to copolymer stability problems and higher processing costs.
• the Applicant was therefore interested in the behavior of block copolymers comprising a biodegradable block.
• the object of the invention is therefore to remedy at least one of the disadvantages of the prior art.
• the invention aims in particular to provide a block copolymer film comprising at least a first biodegradable block, said block copolymer film being capable of nanostructuring in nanodomains with a controlled period of less than 20 nm, after a one-time annealing.
• moderate temperature less than 200 ° C and preferably less than 180 ° C and with a kinetics less than 30 minutes, preferably less than 15 minutes.
• a nano-structured block copolymer film in nano-domains comprising at least a first biodegradable block and a second block of a different chemical nature of the first block, said copolymer characterized in that the first biodegradable block is amorphous and in that the second block is derived from an oligomer or a polymer carrying a hydroxy function on at least one end and acting as a macro-initiator of the polymerization of the first block,
• the first amorphous biodegradable block is of polyester type
• the first amorphous polyester-type biodegradable block is chosen from polymers of ⁇ - or ⁇ -lactones substituted or unsubstituted by aryl or alkyl groups;
• the first amorphous polyester-type biodegradable block is an amorphous caprolactone (PCL am ) copolymer formed from ⁇ -caprolactone and at least one other comonomer selected from ⁇ - or ⁇ -lactones substituted with aryl or alkyl groups ;
• PCL am amorphous caprolactone
• block copolymer is a diblock or triblock copolymer
• the comonomers of constitution of the amorphous caprolactone copolymer are ⁇ -caprolactone ( ⁇ -CL) and 4-phenyl-caprolactone (4-Phl-CL);
• the molar ratio between the ⁇ -CL / 4-Ph ⁇ -CL comonomers is between 6/1 and 3/1, preferably between 6/1 and 4/1;
• the number-average molecular mass of each block of amorphous caprolactone copolymer (PCLam) is between 1000 and 30000 g / mol, preferably between 2000 and 15000 g / mol;
• the number-average molecular weight of the block copolymer is between 7000 and 33000 g / mol
• the second macro-initiator block is derived from a mono- or polyhydroxylated oligomer or polymer chosen from: (alkoxy) polyalkylene glycols, such as (methoxy) polyethylene glycol (MPEG / PEG), polypropylene glycol (PPG) and polytetramethylene glycol (PTMG); poly (alkyl) alkylene adipate diols such as poly (2-methyl-1,3-propylene adipate) diol (PMPA) and poly (1,4-butylene adipate) diol (PBA); polysiloxanes, such as mono or di-hydroxylated polydimethylsiloxane (PDMS), mono or di-carbinols, or optionally hydrogenated mono- or dihydroxylated polydienes, such as
• the term "monomer” as used refers to a molecule that can undergo polymerization.
• polymerization refers to the process of converting a monomer or a mixture of monomers into a polymer.
• oligomer as used refers to a small polymer compound, comprising between 2 and 30 monomers, that is to say, whose degree of polymerization is between 2 and 30.
• copolymer block or “block” is meant a polymer comprising several monomer units of several types, or of the same type.
• block copolymer means a polymer comprising at least two blocks as defined above, the two blocks being different from one another and having a phase segregation parameter such that they are not miscible and separate into nano-domains at a temperature below the degradation temperature of the block copolymer.
• miscibility refers to the ability of two compounds to mix completely to form a homogeneous phase.
• the block copolymer according to the invention advantageously comprises a first biodegradable block, capable of being easily removed after nanostructuration of the copolymer, so as to produce a porous film intended to serve as a nanolithography mask.
• the block copolymer comprises at least one other block, different from the first, and which is incompatible with the first block, that is to say that they can not mix and separate into nano-domains.
• the first biodegradable block has an amorphous structure.
• the first amorphous biodegradable block is of polyester type.
• polyesters capable of forming this first amorphous block for example, amorphous polymers of ⁇ -lactone monosubstituted by linear or branched, optionally substituted aryl or alkyl groups, or amorphous polymers of ⁇ -lactone monosubstituted by groups may be selected.
• This may for example be an amorphous polybutyrolactone type polymer (noted PBL a m), or amorphous polycaroplactone type (noted, for the sake of simplification, PCL am in the following description).
• the first amorphous block is an amorphous polycaprolactone (PCL am ).
• PCL is a semi-crystalline polymer that has a moderate TM (60 ° C) melting temperature and a low T g (-60 ° C) glass transition temperature. Due to these moderate to low temperatures, the applicant has speculated that they would promote a phase segregation of the block copolymer at a moderate annealing temperature, preferably below 200 ° C, and with favorable kinetics, preferably less than 30 minutes.
• the block copolymers comprising a PCL semi-crystalline polycaprolactone block have no nanoscale structuring. Even if these block copolymers nanostructure when they are annealed at a temperature of about 100 ° C for 12 hours, at the time of cooling to room temperature, crystals appear which destroy the nanostructuration of the nanostructures. Block copolymers obtained, so that at room temperature, the block copolymers have no nanostructuration.
• the second block is formed from an oligomer or a polymer whose chemical nature is incompatible with the first block and comprising an alcohol function on at least one end.
• This second functionalized alcohol polymer serves to serve as a macro-initiator for the polymerization of the first block, in particular polycaprolactone in the presence of methanesulfonic acid (AMS) as catalyst.
• AMS methanesulfonic acid
• it comprises only a hydroxyl function on one end, it makes it possible to produce a diblock copolymer with the PCL.
• it comprises a hydroxyl function at both ends it makes it possible to synthesize a triblock copolymer, with PCL blocks at the ends.
• an annealing treatment at a temperature of between 130 and 170 ° C. for a period of time. very short, advantageously less than 10 minutes and preferably between 1 and 5 minutes, is sufficient to observe a nanostructuration in the block copolymer film.
• the treatment of the film by annealing at a temperature below 180 ° C. makes it possible to improve the mobility of the polymer chains and to accelerate the structuring kinetics of the copolymer.
• the amorphous caprolactone copolymer intended to form the first block copolymer polyester block, is obtained by copolymerization of ⁇ '-caprolactone with a monomer of similar nature.
• “nature monomer close to ⁇ ' ⁇ -CL” is meant a monomer of the monosubstituted ⁇ -lactone or monosubstituted ⁇ -lactone type.
• the amorphous PCL is thus formed from ⁇ -caprolactone and from at least one other comonomer selected from ⁇ - or ⁇ -lactones substituted with aryl or alkyl groups.
• 4-Phenyl-caprolactone denoted 4- ⁇ - ⁇ - ⁇ in the rest of the description, is the preferred comonomer, since it makes it possible to render the caprolactone copolymer amorphous to a low molar rate, of the order of 15 to 20%.
• the comonomers of caprolactone and 4-phenyl-caprolactone thus make it possible to form a random copolymer of poly (4-phenyl-caprolactone- ⁇ -caprolactone), hereinafter denoted P (4-Ph---CL-r). - ⁇ -CL).
• the second polymer forming the second block of the block copolymer according to the invention and acting as macro-initiator of the polymerization of the first block, and more particularly of the random copolymer of caprolactone, can advantageously be chosen from an oligomer or a polymer mono- or polyhydroxy, especially chosen from: (alkoxy) polyalkylene glycols, such as (methoxy) polyethylene glycol (MPEG / PEG), polypropylene glycol (PPG) and polytetramethylene glycol (PTMG); poly (alkyl) alkylene adipate diols such as poly (2-methyl-1,3-propylene adipate) diol (PMPA) and poly (1,4-butylene adipate) diol (PBA); polysiloxanes, such as mono or dihydroxylated polydimethyl siloxane (PDMS); mono or di-carbinol, optionally hydrogenated, ⁇ -hydroxylated or ⁇ , ⁇ -d
• the macro-initiator may be a co-oligomer or a vinyl copolymer of the family of acrylic, methacrylic, styrenic or diene polymers, which results from a copolymerization between acrylic monomers, methacrylic, styrenic or dienes and functional monomers having a hydroxyl group, such as hydroxylated acrylic or methacrylic monomers, such as, for example, 4-hydroxybutyl acrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate.
• This polymerization can be carried out according to a conventional free radical process, a controlled radical process or an anionic process.
• the macro-initiator may be a vinyl copolymer obtained by controlled radical polymerization, or not, in which the radical initiator and / or the control agent carry at least one hydroxyl or thiol function.
• the macro-initiator is advantageously chosen from hydroxylated polyolefins, that is to say any polymer derived from olefins bearing at least one hydroxyl function or telechelic hydroxy.
• the polydienes are referred to and among these, polybutadienes are preferred, and especially telechelic hydroxy polybutadiene.
• the telechelic hydroxy polybutadiene is a polymer marketed by Cray Valley under the commercial reference Kraso ® and more particularly Krasol LBH-P3000 ® and Krasol HLBH-P3000 ® .
• the Krasol LBH-P3000 ® is a polybutadiene prepared by anionic polymerization, having an average molecular weight M n is in the range of 3500 g / mol.
• the Krasol HLBH-P3000 ® is a hydrogenated polybutadiene having an average molecular weight M n is in the range of 3100 g / mol.
• Such telechelic hydroxy polybutadienes then act as macro-initiators of the polymerization of the first amorphous block, and more particularly of the constituent comonomers of the amorphous caprolactone copolymer (PCL am ).
• These macro-initiators, dihydroxylated, make it possible to synthesize triblock copolymers of PCL-Krasol®-PCL with a central block of polybutadiene type (PBT) hydrogenated or not.
• PBT polybutadiene type
• the number-average molecular mass of each PCLam amorphous PCL block is advantageously between 1000 and 30000 g / mol and preferably between 2000 and 15000 g / mol.
• the number-average molecular weight of the block copolymer obtained is between 7000 and 33000g / mol.
• the molar ratio in s-CL / 4-Ph-s-CL is between 6 / 1 and 3/1, and preferably between 6/1 and 4/1, which corresponds to a molar percentage of 4-Ph-s-CL preferably between 15 and 20%.
• the block copolymer thus produced is then deposited as a film on a substrate.
• the process for producing such a block copolymer film comprises the steps of synthesizing the block copolymer by mixing the macro-initiator, for example a hydroxylated polyolefin macro-initiator, and more particularly a hydroxylated or di-substituted polybutadiene.
• a PCL block copolymer has m-PBT-PCL m.
• the solvent is advantageously chosen from toluene, ethylbenzene or xylene. Toluene is however preferred to the other two solvents.
• the solvent of the solution is evaporated and the film is annealed at a specified temperature of between 130 and 170 ° C, for a period of less than 30 minutes, and preferably less than 15 minutes, to ensure the nano-structuring of the copolymer in nano-domains perpendicular to the surface to be etched.
• An annealing temperature of between 130 and 170 ° C. is sufficient to obtain nanostructuring in a short period of time of the order of a few minutes, preferably less than 15 minutes, and more preferably less than 5 minutes and ideally 1 to 2 minutes.
• the desired structure for example the generation of nano-domains perpendicular to the surface
• the desired structure requires the preparation of the surface on which the copolymer solution is deposited in order to control surface energy.
• the surface on which the copolymer solution is deposited there is deposited on the surface a random copolymer whose monomers may be identical in whole or in part to those used in the block copolymer that is to be deposited.
• Mansky et al. Science, vol 275 pages 1458-1460, 1997) describes this technology well, now well known to those skilled in the art.
• the preferred surfaces include surfaces made of silicon, silicon having a native or thermal oxide layer, germanium, platinum, tungsten, gold, titanium nitrides, graphenes, BARC (bottom anti-reflective coating) or any other anti-reflective layer used in lithography.
• a solution of the block copolymer according to the invention is deposited and the solvent is evaporated according to techniques known to those skilled in the art such as the so-called “spin coating” technique, “Doctor Blade “,” Knife system “,” slot die System “but any other technique can be used such as a dry deposit, that is to say without going through a prior dissolution.
• a heat treatment is carried out which allows the block copolymer to organize properly, that is to say to obtain in particular a phase separation between the nano-domains whose size is less than 10. nm, with a controlled morphology of the nano-domains and with a period less than 20 nm, a preferential orientation of the domains, perpendicular to the surface to be etched, and a reduction in the number of defects.
• the temperature T of this heat treatment is such that it is less than 180 ° C and higher than the highest glass transition temperature of the blocks constituting the copolymer. It is carried out under a solvent or a thermal atmosphere or by a combination of these two methods.
• the obtained copolymer is a diblock copolymer type am -PBT PCL or PCL triblock a m-PBT-PCL m.
• the synthesis of the block copolymer according to the invention is preferably carried out at a temperature ranging from 20 to 120.degree. C. and more preferably between 30 and 60.degree. especially when the solvent is toluene.
• the macro-initiator is a hydroxytelechelic polybutadiene, hydrogenated or not, it is indeed possible to obtain, at a temperature of the order of 30 ° C., block copolymers of PCLam-b-Krasol®-b-PCLam. or PCLam-b-Krasol® ⁇ - ⁇ -PCL am having an average molecular weight in number M n of up to 33000 g / mol in a few hours and with a yield greater than or equal to 85% after purification.
• the molar ratio initiator / catalyst is preferably between 1/1 and 1/2.
• the reagents used in this process are preferably dried before being used, in particular by vacuum treatment, distillation or drying with an inert desiccant.
• the cylindrical or lamellar morphology of the nano-domains thus formed depends on the molar ratio of ⁇ -CL and 4-Ph---CL co-monomers on the macro-initiator in the initial mixture, but also on the nature of the macro-initiator. initiator forming the second block of the block copolymer and its degree of polymerization.
• the molar ratio of ⁇ -CL and 4-Ph---CL co-monomers with respect to each functional end of the macro-initiator is preferably between 16/1 and 130/1.
• the first block of PCL am is advantageously removed to form a nanolithography mask comprising a porous pattern perpendicular to the surface to be etched and having a Lo ⁇ 20 nm period.
• a block copolymer according to the invention therefore makes it possible to obtain an assembly of the blocks perpendicular to the surface on which it is deposited, with a significant phase segregation, making it possible to obtain nano-domains of small sizes, of the order of a nanometer to a few nanometers and controlled morphology, and a period less than or equal to 20nm.
• Such a block copolymer therefore allows better control of the lithography process whose resolution is high and compatible with the current requirements in terms of component dimensions.
• the copolymers obtained based on amorphous polyester, and more particularly amorphous PCL are capable of segregating at low molar masses, typically between 4000 and 30000 g / mol, by treatment at low annealing temperatures. high ( ⁇ 180 ° C) and in a very short time ( ⁇ 10 min). Well-defined domain morphologies are then obtained with low U periods ( ⁇ 20 nm).
• the sulphonic acid used as catalyst in the copolymerization reaction is methanesulfonic acid (AMS).
• the toluene is dried using a MBraun SPS-800 solvent purifier. Methanesulfonic acid (AMS) was used without further purification. Diisopropyl ethylamine (DIEA) was dried and distilled on Cah and stored on potassium hydroxide (KOH). The ⁇ -caprolactone dried on Cah then distilled is stored under an inert atmosphere. 4-Ph-? -CL was recrystallized with toluene then dried over P2O5 and stored under an inert atmosphere.
• AMS Methanesulfonic acid
• DIEA Diisopropyl ethylamine
• KOH potassium hydroxide
• 4-Ph-? -CL was recrystallized with toluene then dried over P2O5 and stored under an inert atmosphere.
• the Schlenk tubes were dried with a vacuum heat gun to remove any trace of moisture.
• the reaction was monitored by 1 H NMR (proton nuclear magnetic resonance) on Brucker AVANCE devices 300 and 500 and steric exclusion chromatography (SEC) in THF. To do this, samples were taken, neutralized with DIEA (Diisopropylethyl-amine), evaporated and taken up in a suitable solvent for their characterization.
• the spectra are recorded in deuterated chloroform, spectrometer at 300 MHz.
• the number-average molecular weight Mn and the degree of polydispersity (D) of the samples of copolymers taken are measured by steric exclusion chromatography SEC in THF with polystyrene calibration.
• the differential scanning calorimetry measurement, denoted DSC makes it possible to study glass transitions and crystallization.
• DSC the English acronym "Differential Scanning Calorimetry” is a thermal analysis technique to measure the differences in heat exchange between a sample to be analyzed and a reference during phase transitions. To carry out this study, a NETZCH DSC204 differential scanning calorimeter was used.
• the calorimetry analyzes were carried out between -80 and 130 ° C. and the temperature values were recorded during the second temperature rise (at a rate of 10 ° C./min).
• SAXS Small angle X-ray scattering analysis
• This analysis technique consists of diffusing a monochromatic radiation through the sample to be analyzed.
• the scattered intensity is collected as a function of the scattering angle passing through the sample, the scattering angle being very close to the direct beam.
• the scattered photons provide information on the fluctuation of electron densities in the heterogeneous material.
• SAXS analysis a Nanostar SAXS (Bruker) or BM-26B DUBBLE station at the European Synchrotron Radiation Facility (ESFR) was used.
• triblock copolymers based on semi-crystalline polycaprolactone (PCL) on the one hand and based on amorphous poly (£ -CL-co-4-Ph---CL) on the other hand. have been prepared and compared.
• Example 1 (Comparative) Preparation of a triblock copolymer poly (g-caprolactone) April 3-fe / oc-Krasol LBH-P3000-6 / oc-poly (g -caprolactonek3
• the macroinitiator (Krasol LBH-P3000, 1 eq., 1 .5 g) and I ' ⁇ -CL (90 eq., 4.1 1 g) is weighed in a glove box and introduced into a dry schlenk.
• the reaction medium is stirred under argon at 30 ° C. for 2 h 30 min.
• the polymerization reaction of the ⁇ -CL monomer with the macro-initiator is as follows:
• Example 3 (Comparative): Preparation of trifunctional polyfunctional caprolactone copolymer / oc-Krasol HLBH-P3000-6 / oc-poly (g-caprolactone)
• the macroinitiator (Krasol HLBH-P3000, 1 eq., 0.33 g) and I ' ⁇ -CL (70 eq., 0.75 g) are weighed in a glove box and introduced into a dry schlenk.
• the reaction medium is stirred under argon at 30 ° C. for 1 h 30 min.
• the thermal analyzes (DSC) of the copolymers studied show a single glass transition because of the values very close to the T g of the two blocks (PCL, -60 ° C. and Krasol -55 ° C.). Given the proximity of the T g values of the corresponding homopolymers (PCL, -60 ° C and Krasol -55 ° C) it is difficult to conclude as to the ability of these blocks to segregate only with DSC analysis. It should also be noted that the block copolymers comprising the PCL block are semi-crystalline in nature, while those with the PCL am block are amorphous in nature.
• the SAXS analyzes provide more light on the different behavior of the block copolymers according to whether they incorporate end blocks PCL or PCL am .
• PCL polycrystalline
• nano-structuring with a well-defined morphology is observed, in particular with hydrogenated Krasol.
• the nanostructuring morphology is cylindrical for the cases observed and summarized in Table I below.
• FIG. 1 illustrates the curve obtained by SAXS analysis of a PCL AM 65-ib-Krasol film PCL AM 65 with q corresponding to the scattering angle over the wavelength used, * corresponding more particularly to the most intense diffusion.
• the values of q / q * obtained for the different peaks (1, ⁇ / 4, ⁇ / 7, V9) are characteristics of a hexagonal cylindrical arrangement with an average U period of 17.3nm.
• the SAXS analyzes of the block copolymers were carried out on the polymers as obtained during the synthesis-purification, after annealing at 100 ° C. for 12 hours.
• PCLam-6-Krasol-i-PCLam triblock copolymers or PCLam-6-Krasol Hb-PCLam giving rise to nano-structuring, were then selected for analysis by microscopy, more particularly PCLam-b-Krasol Hb. -PCLam.
• a copolymer solution is deposited in the form of a thin film with a thickness of 140 nm on a surface, then the solvent is evaporated and the film is annealed at a temperature between 130 and 170 ° C for a time between 5 and 10 minutes.
• Table I the PCL am.
• the block copolymers incorporating an amorphous caprolactone copolymer polyester block are therefore capable of segregating, giving rise to structuring at the nanometric scale, whereas no nano-structuring is observed for the equivalent triblock copolymers in size, based on semi-crystalline polycaprolactone.
• the copolymers obtained based on PCL am are capable of segregating for low molecular weights, typically less than 33000 g / mol, allowing access to various morphologies according to their composition with periods of structuring. very low value, less than 20 nm.
• the copolymer according to the invention thus differs strongly from conventional PS-b-PMMA block copolymers which do not make it possible to obtain periods lower than 20 nm.

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• 2016
  • 2016-12-14 FR FR1662466A patent/FR3060008A1/fr not_active Ceased
• 2017
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