WO2008065301A1 - Memoire optique 3d comprenant un copolymere a blocs contenant un monomere photoactif porteur d'un groupement photoisomerisable - Google Patents
Memoire optique 3d comprenant un copolymere a blocs contenant un monomere photoactif porteur d'un groupement photoisomerisable Download PDFInfo
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- WO2008065301A1 WO2008065301A1 PCT/FR2007/052398 FR2007052398W WO2008065301A1 WO 2008065301 A1 WO2008065301 A1 WO 2008065301A1 FR 2007052398 W FR2007052398 W FR 2007052398W WO 2008065301 A1 WO2008065301 A1 WO 2008065301A1
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- 0 C1CC*CC1 Chemical compound C1CC*CC1 0.000 description 4
- OIHQJCVBSPCHGM-UHFFFAOYSA-N CCCC1C(CC)CCNC1 Chemical compound CCCC1C(CC)CCNC1 OIHQJCVBSPCHGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/245—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing a polymeric component
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
- G11B7/2467—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes azo-dyes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
Definitions
- 3D optical memory comprising a block copolymer containing a photoactive monomer carrying a photoisomerisable group
- the technology that is contemplated in the present invention is more particularly that of 3-D optical storage as described in international applications WO 01/73779 and WO 03/070689 and in Japanese Journal of Applied Physics. , Flight. 45, No. 28, 2006, pp. 1229-1234. It is based on the use of a photo-isomerizable chromophore which is in two thermodynamically stable isomeric forms, interconvertible under the effect of a light irradiation of appropriate wavelength. When no data has yet been recorded, one of the two forms has a majority. For data writing, this isomeric form is converted to the other by light irradiation having an appropriate wavelength. The conversion may result from a direct or indirect optical interaction (eg multiphoton).
- the present invention relates to a polymer for optical data storage in 3D. It also relates to the material obtained from this polymer as well as to the optical memory in 3D, in particular in disk form.
- the chromophores are attached to a polymer through the (co) polymerization of monomers carrying said chromophores.
- the application WO 2006/075327 also teaches the interest in increasing the concentration of chromophores so as to improve the recording sensitivity of the optical memory.
- concentration of monomers carrying chromophores increases, the mechanical properties of the polymer are affected and the material obtained is either too fragile or too soft to be easily manipulated. The need therefore exists to develop a rigid material that can be used in the field of 3D optical storage having good readability and data rewriting.
- US Patent 5023859 discloses an optical memory based on the use of a polymer carrying a photosensitive group of the stilbene, spiropyran, azobenzene, bisazobenzene, trisazobenzene or azoxybenzene type.
- the polymer may be a block polymer, but there is no further clarification on the exact nature of this block polymer.
- the polymer may be a polyalkylacrylate or a copolymer of the polyalkylacrylate, especially a copolymer with styrene. It may also be polymethyl methacrylate. It is not specified that it may be a block copolymer or that the chromophore is present in one of the blocks in particular.
- the invention relates to a block copolymer comprising:
- At least one block B comprising at least one photoactive monomer carrying a photo-isomerizable chromophore.
- the photoactive monomer has the formula (I):
- X is H or CH 3 -;
- CR denotes a photo-isomerizable chromophore
- the block copolymer makes it possible to obtain a 3D optical memory.
- the invention also relates to the mixture comprising the block copolymer and a polymer which is a thermoplastic, a thermoplastic elastomer or a thermosetting as well as a 3D optical memory comprising the block copolymer.
- T 9 denotes the glass transition temperature of a polymer, measured by DSC according to ASTM E1356.
- the T 9 of a monomer is also referred to as the T 9 of the homopolymer having a number-average molecular weight M n of at least 10,000 g / mol, obtained by radical polymerization of said monomer.
- M n number-average molecular weight
- photoactive monomer is understood to mean a monomer carrying a photo-isomerizable CR chromophore group.
- the chromophore exists in two isomeric forms, for example cis / trans. The conversion from one form to another takes place under the action of a light irradiation of appropriate wavelength.
- the photoactive monomer has the formula (I):
- X is H or CH 3 -;
- CR denotes a photoisomerizable chromophore
- the spacer group L has the function of improving the freedom of movement of the chromophore with respect to the copolymer chain so as to promote the conversion of the chromophore from one form to another. This improves the capacity and speed of reading.
- L is chosen such that G and CR are connected to each other by a sequence of 2 or more atoms which are linked together by covalent bonds.
- L can be chosen for example from the groups (CRiR 2 ) m , O (CRiR 2 ) m , (OCRiR 2 ) m in which m is an integer greater than 2, preferably between 2 and 10 and R 1 and R 2 independently denote H, halogen or linear or branched alkyl or aryl groups.
- R 1 and R 2 denote H.
- the chromophore CR is preferably of the diarylalkylene type existing in cis and trans isomeric forms. It may be one of the chromophores disclosed in WO 01/73779, WO 03/070689, WO 2006/075329 or WO 2006/075327. Preferably, chromophore CR is chosen so that the energy barrier for isomerization is greater than 80 kJ / mol. Indeed, it is desirable that the isomerization is a very slow process at room temperature to avoid a loss of recorded data.
- Ar 1 and Ar 2 denote optionally substituted aryl groups
- W 1 and W 2 are chosen from the groups -CN, -COOH, -COOR ', -OH, -SO 2 R', -NO 2 , R 'being a C 1 -C 10 alkyl or aryl group.
- L is linked by covalent bonds to Ar 2 as well as to G.
- Ar 1 and Ar 2 denote aryl groups, substituted or unsubstituted. They are chosen for example independently of one another from phenyl, anthracene or phenanthrene groups.
- the optional substituent (s) are chosen from: H, C 1 -C 10 alkyl, NO 2 , halogen or C 1 -C 10 alkoxy, NR "R '" with R “and R'” being H or linear or branched C 1 -C 10 alkyl.
- Ar 1 is a phenyl group and Ar 2 is a phenyl or biphenyl group, each of the phenyl and / or biphenyl groups possibly being optionally substituted, that is to say that the chromophore has the formula (V) or ( Vl):
- Optional substituents may be for example H, aryl, linear or branched C 1 - Co, NO 2, halogen or alkoxy, C 1 -C 10.
- W 1 and W 2 are CN, Ar 2 is phenyl, Ar 1 is phenyl substituted para-R 5 O-.
- R 5 denotes a linear or branched alkyl or aryl group, substituted or unsubstituted.
- R 5 is a linear or branched C 1 -C 4 alkyl group.
- R 5 may be, for example, a methyl, ethyl, propyl or butyl group.
- it may be the chromophore of formula (VII):
- W 1 and W 2 denote CN
- Ar 2 is a phenyl group
- Ar 1 is a biphenyl group substituted by R 5 O-.
- it may be the chromophore of formula (VIII):
- the trans isomer has a greater fluorescence than cis; the trans isomer has a large biphotonic absorption cross section; the Stokes shift (“Stokes shift”) is greater than 100 nm (little overlap between the absorption and emission spectra with peaks respectively at 375 and 485 nm).
- Chromophores which have a low overlap, i.e. ⁇ 35% or even better ⁇ 20%, between the absorption and emission spectra are preferred (see, on this, page 22 of WO 2006/075327). . This makes it possible to increase the concentration of the chromophore thus to favor the cooperative effect without impairing the quality of the signal during the reading.
- the overlap depends on both the Stokes displacement and the peak width.
- the overlap is defined as the absorbed emission percentage for a solution of the 0.01 M chromophore in a 1 cm passage vessel.
- the Stokes shift is> 100 nm.
- the invention is not limited to the particular chromophores of diarylalkylene type but can also be applied to other photoisomerizable chromophores, not including stilbene, spiropyran, azobenzene, bisazobenzene, trisazobenzene or azoxybenzene.
- a list of these chromophores can be found in the following documents US 5023859, US 6875833 and US 6641889.
- cooperative effect monomer means a compound of formula (VIII):
- Ar 3 denotes an aromatic group substituted by at least one inducing substituent (-I).
- This monomer interacts by a cooperative effect with the chromophore and / or improves the cooperative effect between the chromophores themselves, which improves the writing speed.
- An interpretation of the cooperative effect is that the monomer modifies the micro-environment of the chromophore and promotes photo-isomerization.
- the inducing substituent (-I) is chosen from: (i) halogens;
- Ar 3 is a phenyl group.
- the halogen group is chlorine.
- Ar 3 is chosen from the following groups:
- hindered monomers may be used:
- TCLP and TCLPa refer to methacrylate and 2,4,6-trichlorophenoxypropyl acrylate, respectively.
- this block can be rigid or soft. It has a T 9 > -60 ° C, preferably a T 9 > O 0 C, advantageously> 60 ° C, for example> 80 ° C. Preferably, it also has a mass average number Mn> 2000 g / mol, advantageously> 5000 g / mol, preferably> 10000 g / mol, and for example> 50000 g / mol.
- the modulus of elasticity of the block is preferably> 100 MPa, advantageously> 500 MPa, preferably> 1000 MPa.
- One of the functions of block A is to obtain a sufficient mechanical strength of the block copolymer.
- Block A is obtained from the polymerization of at least one vinyl, vinylidene, diene, olefinic, allylic or (meth) acrylic monomer.
- This monomer is chosen more particularly from vinylaromatic monomers such as styrene or substituted styrenes, especially alpha-methylstyrene, acrylic monomers such as acrylic acid or its salts, alkyl acrylates, cycloalkyl acrylates or aryl acrylates.
- hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate
- ether alkyl acrylates such as acrylate methoxyethyl, alkoxy- or aryloxy-polyalkylene glycol acrylates such as methoxypolyethylene glycol acrylates, ethoxypolyethylene glycol acrylates, methoxypolypropylene glycol acrylates, methoxy-polyethylene glycol-polypropylene glycol acrylates or mixtures thereof
- aminoalkyl acrylates such as 2- (dimethylamino) ethyl acrylate (ADAME), fluorinated acrylates, silyl acrylates, phosphorus acrylates such as phosphate acrylates alkylene glycol, methacrylic monomers such as methacrylic acid or its salts, alkyl, cycloalkyl, al
- Block A is preferably obtained from styrene and / or (meth) acrylic monomer (s) and / or butyl acrylate.
- the block A comprises as major monomer (s) styrene and / or MMA and / or butyl acrylate.
- it comprises from 80 to 100% styrene and / or MMA and / or butyl acrylate.
- Block A is intended to confer the mechanical properties of strength and / or rigidity of the finished material.
- block A can comprise, by weight, from 80 to 100% of styrene and / or MAM, from 0 to 10% of at least one comonomer chosen from the list defined above and from 1 to 10% at least one photoactive monomer, the total being 100%.
- the comonomer must be copolymerizable with styrene and / or MAM as well as with the photoactive monomer.
- block B it comprises at least one photoactive monomer and optionally at least one other monomer copolymerizable with the photoactive monomer.
- the other monomer may be chosen from the list of monomers defined above. It can also be a monomer with a cooperative effect.
- the content by weight of photoactive monomer in block B may range from 5 to 100%.
- the monomer that is copolymerized with the photoactive monomer is a cooperative effect monomer. It is preferably TCLP or TCLPa.
- Block B therefore comprises by weight 10 to 80% of at least one photoactive monomer, 10 to 80% of at least one synergistic monomer and optionally a monomer 3rd selected from the previous list (the total making 100 %).
- 3rd monomer there can be used a monomer T 9 ⁇ 0 ° C, advantageously ⁇ -2O 0 C, more preferably ⁇ - 40 0 C, for example butyl acrylate (Examples 3 and 4 illustrate this preferred form) or> 0 0 C such as methyl methacrylate.
- the block copolymer of the invention it comprises at least one block A and at least one block B comprising at least one photoactive monomer.
- a block copolymer consists of adjacent blocks that are constitutionally different, ie, blocks comprising units derived from different monomers or the same monomer, but according to a composition or a sequential distribution of different patterns.
- a block copolymer may for example be a diblock, triblock or star copolymer.
- the block copolymer is such that block (s) A and block (es) B are incompatible, that is to say that they have a Flory interaction parameter. -Huggins X AB 11 O at room temperature. This results in phase microseparation with the formation of a two-phase structure on a macroscopic scale.
- the block copolymer is then nanostructured, that is to say that domains are formed whose size is less than 100 nm, preferably between 10 and 50 nm. Nanostructuring has the advantage of leading to a transparent material. In addition, this makes it possible to obtain domains concentrated in chromophores because there is no "dilution" by the block (s) A, which makes it possible to promote the cooperative effect between chromophores (with an increase in the writing speed).
- the block copolymer is preferably a triblock copolymer A-B-A 'comprising a central block B connected by covalent bonds to two side blocks A and A' (that is to say arranged on each side of the central block B).
- a and A ' may be the same or different (this type of copolymer is sometimes also noted A-b-B-b-A').
- It may also be a triblock copolymer BAB 'comprising a central block A connected by covalent bonds to two lateral blocks B and B' (that is to say placed on each side of the central block A) and which include chromophore patterns.
- B and B ' may be the same or different.
- the blocks A and A ' comprise, as the major monomer (s), styrene and / or MMA and / or butyl acrylate;
- the blocks B and B ' comprise, by weight, from 10 to 60% of at least one photoactive monomer, from 10 to 60% of at least one co-operative monomer and optionally a monomer from the preceding list (the total %), which is preferably an alkyl (meth) acrylate, more particularly methyl methacrylate.
- the block copolymer may be used alone or in admixture with another polymer which has sufficient transparency in the wavelength range used for writing or reading as well as low birefringence. It can be a thermoplastic, a thermoplastic elastomer or a thermosetting. This characteristic is important for the 3D optical memory technology for which it is necessary for the light ray to reach each layer of the memory without being disturbed.
- thermoplastic such as a homo- or copolymer of methyl methacrylate or styrene or a polycarbonate is preferably used.
- the mixture comprises, by weight, from 50 to 100%, advantageously from 75 to 100%, preferably from 90 to 100%, of the block copolymer, respectively from 0 to 50%, advantageously from 0 to 25%, preferably 5 to 10%. % of the thermoplastic.
- the mixture is obtained using all the thermoplastic blending techniques known to those skilled in the art. It is preferably extrusion.
- the block copolymer and / or the mixture may also optionally comprise various additives (antistatic, lubricant, colorant, plasticizer, antioxidant, anti-UV, etc.).
- the block copolymer is obtained using polymerization techniques known to those skilled in the art.
- One of these polymerization techniques may be anionic polymerization as it is for example taught in the following documents FR 2762604, FR 2761997 and FR 2761995. It may also be the controlled radical polymerization technique which comprises several variants depending on the nature of the control agent that is used.
- SFRP Stable Free Radical Polymerization
- ATRP Atom Transfer Radical Polymerization
- RAFT Reversible Addition Fragmentation Transfer
- sulfur-containing products such as dithioesters, trithiocarbonates, xanthates or dithiocarbamates.
- Controlled radical polymerization with T nitroxide control is the preferred technique for obtaining the block copolymer of the invention. Indeed, this technique does not require working under conditions as severe as the anionic polymerization (that is to say, no moisture, temperature ⁇ 100 0 C). It also makes it possible to polymerize a wide range of monomers. It can be conducted under various conditions, for example by mass, solvent or dispersed medium such as suspension or emulsion in water.
- stable free radical denotes a radical that is so persistent and non-reactive with respect to air and moisture in the ambient air that it can be handled and stored for a much longer period than the majority free radicals (see Accounts of Chemical Research 1976, 9, 13-19).
- the stable free radical is thus distinguished from free radicals whose lifetime is ephemeral (from a few milliseconds to a few seconds) such as free radicals from conventional polymerization initiators such as peroxides, hydroperoxides or azo initiators. Free radicals initiating polymerization tend to accelerate polymerization whereas stable free radicals generally tend to slow it down. It can be said that a free radical is stable within the meaning of the present invention if it is not a polymerization initiator and if, under the usual conditions of the invention, the average lifetime of the radical is at least one minute.
- the nitroxide T is represented by the structure (IX):
- R 6 , R 7 , R 8 , R 9 , R 10 and R 11 denote linear or branched C 1 -C 20 and preferably C 1 -C 10 alkyl groups, such as methyl, ethyl, propyl or butyl. isopropyl, isobutyl, tert-butyl, neopentyl, substituted or unsubstituted, substituted or unsubstituted C 6 -C 30 aryls such as benzyl, aryl (phenyl), cyclic saturated C 1 -C 30 and wherein the groups R 6 and R 9 may be part of an optionally substituted cyclic structure R 6 -CNC-R 9 which may be chosen from:
- x denoting an integer between 1 and 12.
- R a and R b denote identical or different alkyl groups having from 1 to 40 carbon atoms, optionally linked to each other so as to form a ring and optionally substituted with hydroxyl, alkoxy or amino groups,
- R L denoting a monovalent group of molar mass greater than 16 g / mol, preferably greater than 30 g / mol.
- the group R L may for example have a molar mass of between 40 and 450 g / mol. It is preferably a phosphorus group of general formula (Xl):
- Z 1 and Z 2 which may be the same or different, may be chosen from alkyl, cycloalkyl, alkoxyl, aryloxyl, aryl, aralkyloxy, perfluoroalkyl and aralkyl radicals and may comprise from 1 to 20 carbon atoms (the group or the alkyl part being linear or branched); Z 1 and / or Z 2 may also be a halogen atom such as a chlorine, bromine or fluorine atom.
- R L is a phosphonate group of formula:
- R c and R d are two identical or different alkyl groups, optionally linked so as to form a ring, comprising from 1 to 40 carbon atoms, optionally substituted or not.
- the R L group may also comprise at least one aromatic ring such as the phenyl radical or the naphthyl radical, substituted for example by one or more linear or branched (in) alkyl radicals comprising from 1 to 10 carbon atoms.
- the nitroxides of formula (X) are preferred because they make it possible to obtain good control of the radical polymerization of (meth) acrylic monomers.
- Alkoxyamines of formula (XIII) are preferred:
- Z denotes a multivalent group and o denotes an integer between 1 and 10.
- Z is a group capable of releasing a plurality of radical sites after thermal activation and disruption of the covalent ZT bond. Examples of Z groupings are on pages 15 to 18 of International Application WO 2006/061523.
- Z is a divalent group, i.e. the integer o is 2.
- the central block is first prepared by polymerizing with the alkoxyamine the monomer mixture leading to the central block.
- the polymerization takes place with or without a solvent or in a dispersed medium.
- the mixture is heated to a temperature above the activation temperature of the alkoxyamine.
- the monomer (s) leading to the side blocks is added. It is possible that at the end of the preparation of the central block, there remain monomers not completely consumed that we can choose to eliminate or not before the preparation of the side blocks.
- the removal may for example consist of precipitating in a non-solvent, recovering and drying the central block. If one chooses not to remove the monomers not entirely consumed, they can polymerize with the monomers introduced to prepare the side blocks.
- the optical principles underlying the present invention are the same as those described in international applications WO 01/73779 and WO 03/070689 already published.
- the writing is based on the conversion of one isomeric form to another under the effect of a light irradiation.
- the conversion requires having a chromophore in an excited state, which requires absorption at an energy level E.
- the absorption of two photons is facilitated by combining the energy of at least two photons of one or more photons.
- a plurality of light beams (x) having energy levels E 1 and E 2 which may be different from E.
- the two light beams are in the UV, visible or near-infrared range.
- the conversion is the result of a two-photon absorption process.
- the reading may be based on a linear or non-linear electronic excitation process.
- the emission spectra of the two isomers are different and the emission is collected using a suitable reading device.
- a non-linear process such as Raman scattering or a Four Wave Mixing Process (“Four Wave Mixing Process") can be employed.
- a small volume element of the 3D memory contains the chromophores in a major isomeric form or else under the other.
- the volume element therefore contains information stored in a well-defined and localized area of the memory and is characterized by an optical signal different from that of its immediate environment.
- the invention also relates to the 3D optical memory (or 3D optical storage unit) comprising the block copolymer or the mixture of the invention and which is used to record (store) the data.
- a 3D memory is a memory that stores data at any point (defined by three coordinates x, y and z) of the volume of the memory.
- a 3D memory allows storage of data in several virtual layers (or virtual levels). The volume of the 3D memory is therefore related to the physical volume occupied by it.
- the 3D memory can be obtained by injecting the block copolymer or the mixture.
- This transformation technique is known and converters consists in injecting under pressure the material to melt into a mold (in this connection, reference may be made to Precis plastics, Nathan, 4th edition, ISBN 2-12- 355352-2, pp. 141-156). The material is melted and compressed using an extruder. It is also possible to superpose several layers comprising the block copolymer or the mixture of the invention as taught in the international application WO 2006/075329.
- the optical memory 3D is in the form of a disk which makes it possible to set it in rotation, the writing or reading head being substantially fixed.
- the disc may be obtained by injection or molding of the block copolymer or the mixture if it has the appropriate mechanical characteristics. It can also be obtained by depositing the block copolymer or the mixture on a rigid and transparent support in the range of wavelengths used for writing and / or reading.
- the BLOCBUILDER ® corresponds to the product of formula: example 1 preparation of a dialkoxyamine difunctional
- a triblock copolymer P (MMA co eAA) -bP (butyl acrylate eAA) -bP (MMA co eAA) step 1 5 g eAA, 45 g of butyl acrylate and 0 are introduced under an inert atmosphere. 99 g of the above alkoxyamine in a 100 ml reactor stirred at 400 rpm, and the mixture is heated for 5 h at 115 ° C. At the end of this stage, the conversion of the monomers is 60%. The residual butyl acrylate is evaporated under vacuum. The eAA monomer which is not consumed is not evaporable under vacuum.
- step 2 5.75 g of the mixture of step 1 (ie the polymer and the residual eAA monomer which is not evaporated), 38.3 g of methyl methacrylate and 36 g are introduced. of toluene in a 100 cm 3 reactor stirred at 400 rev / min and under an inert atmosphere and this mixture is heated for 1 h 30 at 105 0 C, then 1 h 30 at 12O 0 C.
- the unreacted methyl methacrylate is evaporated under vacuum, as is toluene.
- the product obtained is a triblock copolymer P (MMA co eAA) -b-P (butyl acrylate eAA) -b-P (MMA co eAA).
- BAB copolymer block B: eMMA / TCLP / rigid block A butyl acrylate copolymer: polystyrene
- the final product is a mixture of the BAB block copolymer and a B copolymer.
- Butyl acrylate makes it possible to correct the refractive index of the TCLP / eMMA system with respect to the PS block polystyrene in order to avoid the formation of haze.
- the mixture is cooled, the mixture is withdrawn and the solvent and the unreacted styrene are evaporated off.
- the polymer solutions obtained in Examples 1 to 4 are precipitated in a large amount of methanol at room temperature, filtered, washed and dried.
- the product obtained is then shaped by compression-molding at 15O 0 C for 10 min to form a disc of 2 cm in diameter and 2 mm thick.
- the light transmission is greater than 90% over the entire visible range.
- This disk is then subjected to a static read-write test of data using a suitable laser device. There was a recording of the data on the disc.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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EP07866542A EP2094751A1 (fr) | 2006-11-28 | 2007-11-26 | Memoire optique 3d comprenant un copolymere a blocs contenant un monomere photoactif porteur d'un groupement photoisomerisable |
JP2009538753A JP2010511089A (ja) | 2006-11-28 | 2007-11-26 | 光異性化が可能な基を有する光活性モノマーを含むブロックコポリマーから成る光学式三次元(3d)記録装置 |
US12/514,781 US20100119761A1 (en) | 2006-11-28 | 2007-11-26 | Optical 3d memory comprising a block copolymer containing a photoactive monomer having a photoisomerable group |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0655154A FR2909093B1 (fr) | 2006-11-28 | 2006-11-28 | Memoire optique 3d comprenant un copolymere a blocs contenant un monomere photoactif porteur d'un groupement photoisomerisable. |
FR06.55154 | 2006-11-28 |
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PCT/FR2007/052398 WO2008065301A1 (fr) | 2006-11-28 | 2007-11-26 | Memoire optique 3d comprenant un copolymere a blocs contenant un monomere photoactif porteur d'un groupement photoisomerisable |
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US (1) | US20100119761A1 (fr) |
EP (1) | EP2094751A1 (fr) |
JP (1) | JP2010511089A (fr) |
KR (1) | KR20090075744A (fr) |
FR (1) | FR2909093B1 (fr) |
WO (1) | WO2008065301A1 (fr) |
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FR2931827A1 (fr) * | 2008-05-27 | 2009-12-04 | Arkema France | Copolymere a blocs contenant un monomere photoactif porteur d'un groupement photoisomerisable, son utilisation dans une memoire optique 3d. |
BR112014004403A2 (pt) * | 2011-08-25 | 2017-03-21 | Rolic Ag | compostos fotorreativos |
CN106232652A (zh) * | 2014-04-21 | 2016-12-14 | 日立化成株式会社 | 嵌段聚合物 |
CN106957384B (zh) * | 2017-03-20 | 2021-07-20 | 内蒙古师范大学 | 一种高灵敏智能调控湿度的材料的制备方法 |
CA3063516A1 (fr) | 2017-05-18 | 2018-11-22 | Eni S.P.A. | Composition polymere comprenant un colorant fluorescent, son procede de preparation, son utilisation et objet le comprenant |
CN110586039B (zh) * | 2019-10-24 | 2020-11-10 | 福州大学 | 一种可用光照再生的生物质吸附剂及其制备方法和应用 |
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EP0286376A2 (fr) * | 1987-04-07 | 1988-10-12 | Mitsubishi Petrochemical Co., Ltd. | Copolymères séquencés du type ABA |
US5023859A (en) * | 1988-03-30 | 1991-06-11 | Rohm Gmbh Chemische Fabrik | Optical data storage apparatus and method utilizing an amorphous polymer which exhibits photochromic properties |
US5837749A (en) * | 1996-04-26 | 1998-11-17 | Shell Oil Company | Non-aqueous solvent free process for making UV curable adhesives and sealants from epoxidized monohydroxylated diene polymers (III) |
US5932663A (en) * | 1995-11-15 | 1999-08-03 | Basf Aktiengesellschaft | Block copolymer and preparation thereof by anionic polymerization |
WO2003070689A2 (fr) * | 2002-02-21 | 2003-08-28 | Mempile Inc. | Composes donateur-accepteur-donateur lies a un polymere et leur utilisation dans une memoire optique tridimensionnelle |
US6673850B1 (en) * | 1999-05-10 | 2004-01-06 | Ciba Specialty Chemicals Corporation | Photoinitiators and their applications |
WO2006075327A1 (fr) * | 2005-01-12 | 2006-07-20 | Mempile Inc. | Disques ameliores pour stockage de donnees |
WO2006075326A1 (fr) * | 2005-01-12 | 2006-07-20 | Mempile Inc. | Additifs de chauffage pour memoire optique tridimensionnelle |
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DE4232394A1 (de) * | 1992-09-26 | 1994-03-31 | Basf Ag | Copolymerisate mit nichtlinear optischen Eigenschaften und deren Verwendung |
US5763548A (en) * | 1995-03-31 | 1998-06-09 | Carnegie-Mellon University | (Co)polymers and a novel polymerization process based on atom (or group) transfer radical polymerization |
US5789487A (en) * | 1996-07-10 | 1998-08-04 | Carnegie-Mellon University | Preparation of novel homo- and copolymers using atom transfer radical polymerization |
DE19720288A1 (de) * | 1997-05-15 | 1998-11-19 | Bayer Ag | Homopolymere mit hoher photoinduzierbarer Doppelbrechung |
CN1513176A (zh) * | 2001-03-28 | 2004-07-14 | 拜尔公司 | 在信息层中含有三氮菁染料作为吸光性化合物的光学数据存储介质 |
-
2006
- 2006-11-28 FR FR0655154A patent/FR2909093B1/fr not_active Expired - Fee Related
-
2007
- 2007-11-26 US US12/514,781 patent/US20100119761A1/en not_active Abandoned
- 2007-11-26 KR KR1020097010900A patent/KR20090075744A/ko not_active Application Discontinuation
- 2007-11-26 WO PCT/FR2007/052398 patent/WO2008065301A1/fr active Application Filing
- 2007-11-26 JP JP2009538753A patent/JP2010511089A/ja active Pending
- 2007-11-26 EP EP07866542A patent/EP2094751A1/fr not_active Withdrawn
Patent Citations (9)
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US3355513A (en) * | 1961-04-27 | 1967-11-28 | Centre Nat Rech Scient | Mesomorphic phase polymers |
EP0286376A2 (fr) * | 1987-04-07 | 1988-10-12 | Mitsubishi Petrochemical Co., Ltd. | Copolymères séquencés du type ABA |
US5023859A (en) * | 1988-03-30 | 1991-06-11 | Rohm Gmbh Chemische Fabrik | Optical data storage apparatus and method utilizing an amorphous polymer which exhibits photochromic properties |
US5932663A (en) * | 1995-11-15 | 1999-08-03 | Basf Aktiengesellschaft | Block copolymer and preparation thereof by anionic polymerization |
US5837749A (en) * | 1996-04-26 | 1998-11-17 | Shell Oil Company | Non-aqueous solvent free process for making UV curable adhesives and sealants from epoxidized monohydroxylated diene polymers (III) |
US6673850B1 (en) * | 1999-05-10 | 2004-01-06 | Ciba Specialty Chemicals Corporation | Photoinitiators and their applications |
WO2003070689A2 (fr) * | 2002-02-21 | 2003-08-28 | Mempile Inc. | Composes donateur-accepteur-donateur lies a un polymere et leur utilisation dans une memoire optique tridimensionnelle |
WO2006075327A1 (fr) * | 2005-01-12 | 2006-07-20 | Mempile Inc. | Disques ameliores pour stockage de donnees |
WO2006075326A1 (fr) * | 2005-01-12 | 2006-07-20 | Mempile Inc. | Additifs de chauffage pour memoire optique tridimensionnelle |
Also Published As
Publication number | Publication date |
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KR20090075744A (ko) | 2009-07-08 |
FR2909093B1 (fr) | 2012-07-13 |
JP2010511089A (ja) | 2010-04-08 |
EP2094751A1 (fr) | 2009-09-02 |
FR2909093A1 (fr) | 2008-05-30 |
US20100119761A1 (en) | 2010-05-13 |
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