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WO2024232370A1 - Polymère, et composé insaturé - Google Patents

Polymère, et composé insaturé Download PDF

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Publication number
WO2024232370A1
WO2024232370A1 PCT/JP2024/017026 JP2024017026W WO2024232370A1 WO 2024232370 A1 WO2024232370 A1 WO 2024232370A1 JP 2024017026 W JP2024017026 W JP 2024017026W WO 2024232370 A1 WO2024232370 A1 WO 2024232370A1
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Prior art keywords
carbon atoms
polymer
group
compound
alkyl group
Prior art date
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English (en)
Japanese (ja)
Inventor
義徳 ▲高▼島
浩 宇山
章秀 菅原
峻秀 朴
崚平 以倉
直巳 竹中
文章 久禮
佑弥 高橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyoeisha Chemical Co Ltd
University of Osaka NUC
Original Assignee
Kyoeisha Chemical Co Ltd
Osaka University NUC
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Priority to JP2024571194A priority Critical patent/JPWO2024232370A1/ja
Publication of WO2024232370A1 publication Critical patent/WO2024232370A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloylmorpholine
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • 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

Definitions

  • the present invention relates to a polymer and an unsaturated compound having a cyclodextrin skeleton.
  • Aliphatic polyesters such as polycaprolactone (PCL) are being considered as resins with low environmental impact because they are biodegradable. They can also be decomposed and recombined using enzymes, so they are attracting attention from the perspective of being reusable through recycling.
  • PCL polycaprolactone
  • Polymer materials having a cyclic molecule cyclodextrin (CD) in the side chain are known (for example, see Patent Document 2).
  • CD cyclic molecule cyclodextrin
  • the polymer main chain penetrates the CD ring to form crosslinks, and the crosslinks by CD perform a sliding motion when stress is applied, thereby exhibiting high stress dispersion.
  • studies have been conducted mainly on acrylic resins, but not on polyester resins.
  • Non-Patent Document 1 describes the use of a polyurethane resin as a polymer having cyclic cyclodextrin in the side chain. However, there is no mention of the modification of aliphatic polyester resins.
  • the objective of the present invention is to provide a polymer having an aliphatic polyester resin skeleton that is biodegradable while also having excellent performance in terms of strength and flexibility.
  • the present invention is a polymer characterized by having a cyclodextrin skeleton as a side chain of the polymer and having a fatty acid polyester resin structure at least in part.
  • the fatty acid polyester resin structure is preferably polycaprolactone.
  • the cyclodextrin skeleton is (In the formula, R 1 's may be the same or different and represent a hydrogen atom, an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 (R 2 is an alkyl group having 1 to 20 carbon atoms), and 20% or more of R 1's are any one of an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 .
  • x is an integer from 5 to 7) It is preferable that:
  • the polymer of the present invention preferably has structural units derived from a compound (A) having a functional group reactive with two isocyanate groups present in a cyclodextrin skeleton and in a structure other than the cyclodextrin skeleton, an aliphatic polyester (B), and a diisocyanate compound (C).
  • R 1 's may be the same or different and represent a hydrogen atom, an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 (R 2 is an alkyl group having 1 to 20 carbon atoms), and 20% or more of R 1's are any one of an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 .
  • x is an integer from 5 to 7
  • the compound is represented by the following formula:
  • the aliphatic polyester (B) is preferably a polycaprolactone having a skeleton derived from a diol compound in part.
  • the polymer of the present invention may be obtained by polymerizing ⁇ -caprolactone in the presence of an acrylic polymer having a cyclodextrin skeleton as a side chain of the polymer.
  • the polymerization of ⁇ -caprolactone is preferably carried out in the presence of a diol compound.
  • the present invention also relates to an unsaturated compound having a structure represented by the following general formula (11):
  • R 1 is (A) The following general formula (12): -R 3 -NH-R 4 (12) ( R3 is an alkylene group having 3 to 20 carbon atoms, which may be linear or branched, and may have a substituent. R4 is a structure represented by the following formula:
  • R 10 represents hydrogen or a methyl group.
  • R5 is an alkylene group having 3 to 20 carbon atoms, which may be linear or branched and may have a substituent.
  • R6 is the same as R4 above. or
  • R2 represents a hydrogen atom, an acyl group having 2 to 50 carbon atoms, or an alkyl group having 1 to 30 carbon atoms.
  • Rc represents a group represented by the following general formula (1).
  • R 1 's may be the same or different and represent an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 (R 2 is an alkyl group having 1 to 20 carbon atoms), and 20% or more of R 1's are any one of an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 .
  • x is an integer from 5 to 7)
  • the resin composition of the present invention is mainly composed of an aliphatic polyester skeleton that has a small environmental impact, and yet has both elasticity and toughness properties.
  • FIG. 2 is a diagram showing the shape of a tensile test sample.
  • 1H NMR of SH-2-DiOH 500 MHz, 25°C
  • 1 H NMR of PCL 1.5 k -diOH 500 MHz, 25°C
  • 13C NMR of PCL 1.5k -diOH 125 MHz, 25°C
  • 1 H NMR of PCL 2.4 k -diOH 500 MHz, 25°C
  • 13C NMR of PCL 2.4 k -diOH 125 MHz, 25°C
  • 1 H NMR of PCL 3.5 k -diOH 500 MHz, 25°C
  • 13C NMR (125 MHz, 25°C) of PCL 3.5 k -diOH 500 MHz, 25°C.
  • FIG. 1 shows the results of an enzymatic decomposition reaction.
  • FIG. 1 shows the results of an enzymatic polymerization reaction.
  • FIG. 1 shows the results of an enzymatic polymerization reaction. Stress-strain curve of polymer using SH-02-siOH. Toughness and Young's modulus of polymers using SH-02-siOH. 1 is a schematic diagram showing a method of heat pressing. In the figure, Teflon is a registered trademark.
  • FIG. 2 is a diagram showing the shape of a tensile test sample.
  • the polymer of the present invention has an aliphatic polyester skeleton as a main structural unit, and in order to improve its physical properties, the polymer has a cyclodextrin skeleton in the side chain.
  • the cyclodextrin ring has excellent elastic properties because the polymer main chain penetrates its center. Furthermore, when stress is applied, the bond is not broken, and the ring structure moves along the main chain to accommodate deformation due to stress. Therefore, the physical properties are not deteriorated by the bond breaking, and it is possible to achieve both excellent elasticity and strength, which are properties that are normally difficult to achieve at the same time.
  • the polymer side chain has a cyclodextrin ring.
  • a cyclodextrin ring preferably has a structure represented by the following general formula (1).
  • R 1 's may be the same or different and represent a hydrogen atom, an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 (R 2 is an alkyl group having 1 to 20 carbon atoms), and 20% or more of R 1's are either an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 .
  • x is an integer from 5 to 7)
  • the compound represented by the above general formula (1) is preferably one in which 20% or more of the hydroxyl groups bonded to the cyclodextrin ring are replaced with hydrophobic groups.
  • the main skeleton of the compound is a hydrophobic aliphatic polyester resin, it is preferable that the hydroxyl groups of the cyclodextrin ring are hydrophobized, in terms of increasing compatibility and improving physical properties.
  • R 1 are either an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 , and further preferably 90% or more.
  • R 1 There is no particular upper limit, and all hydroxyl groups may be substituted.
  • the cyclodextrin represented by the above general formula (1) may have a part or all of the hydroxyl groups substituted with R1 groups in the proportions as described above.
  • R can be at least one group selected from the group consisting of an acetyl group, an alkyl group having 50 or less carbon atoms, and -CONHR (R is a methyl group or an ethyl group). Such substitution can be carried out by a known method.
  • the cyclodextrin skeleton is preferably contained in a proportion of 0.1 mol to 10 mol % relative to the total amount of the polymer. By being contained in such a proportion, favorable effects can be obtained.
  • the lower limit is more preferably 0.2 mol %, and even more preferably 0.3 mol %.
  • the upper limit is more preferably 8.0 mol %, and even more preferably 7.0 mol %.
  • the polymer of the present invention has an aliphatic polyester as a main structural unit.
  • the polymer has a structural unit based on an aliphatic polyester as the main chain skeleton.
  • Aliphatic polyester is known as a resin having biodegradability, and by using this as a main structural unit, a polymer with low environmental impact can be obtained.
  • aliphatic polyesters can be decomposed into low molecular weight compounds by enzymatic degradation. Furthermore, the enzymatic degradation products can be regenerated into polymers by enzymatic reactions. Therefore, discarded polymers can be treated by enzymatic degradation to produce low molecular weight compounds. The low molecular weight compounds thus recovered can then be subjected to an ester bond formation reaction again to regenerate the polymers of the present invention.
  • Non-Patent Document 1 discloses a polymer in which polyether is the main structural unit.
  • polyester By using polyester as the main structural unit, it is preferable in that it has better weather resistance and chemical resistance than a case in which a polyol system is the main skeleton.
  • Such aliphatic polyesters may be obtained by polymerization of hydroxycarboxylic acids or ring-opening polymerization of lactams, or may be obtained by polycondensation of aliphatic dicarboxylic acids and aliphatic diols. They may also be copolymers of these.
  • aliphatic polyesters include polycaprolactone, polylactic acid, poly(1,4-butylene adipate), poly(ethylene adipate), etc.
  • the aliphatic polyester When the aliphatic polyester is mainly composed of polycaprolactone, it may contain a constituent unit consisting of a diol compound in part. That is,
  • n 1 to 29 m is 29 to 1 n + m ⁇ 30
  • the structural unit may be a polycaprolactone represented by the formula: This type of polycaprolactone is preferred because it is easy to synthesize and both polyester terminals are hydroxyl groups.
  • the diol compound has a structural unit based on a diol compound represented by the general formula: Although there is no particular limitation on such a diol compound, for example, one having a molecular weight of 4,000 or less is preferable.
  • ethylene glycol diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, triethanolamine, N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, etc.
  • the physical properties of the polymer of the present invention are significantly different depending on whether the cyclodextrin skeleton is a ⁇ -type or a ⁇ -type.
  • the physical properties of the polymer are also different from those of the polymer described in Non-Patent Document 1, which has a polyether as the basic skeleton.
  • the elongation can be 500 to 10,000%.
  • the lower limit is more preferably 1,000%, and even more preferably 1,500%.
  • the upper limit is more preferably 5,000%, and even more preferably 3,000%.
  • the breaking strength can be 10 to 200 MPa.
  • the lower limit is more preferably 20 MPa, and even more preferably 30 MPa.
  • the upper limit is more preferably 150 MPa, and even more preferably 100 MPa.
  • the Young's modulus can be 10 to 100 MPa.
  • the lower limit is more preferably 20 MPa.
  • the upper limit is more preferably 80 MPa.
  • the toughness can be 100 to 1000 MJm- 3 .
  • the lower limit is more preferably 150 MJm -3 .
  • the upper limit is more preferably 700 MJm -3 .
  • the elongation can be 500 to 10,000%.
  • the lower limit is more preferably 1,000%, and even more preferably 1,500%.
  • the upper limit is more preferably 5,000%, and even more preferably 3,000%.
  • the breaking strength can be 5 to 100 MPa.
  • the lower limit is more preferably 10 MPa.
  • the upper limit is more preferably 70 MPa.
  • the Young's modulus can be 20 to 200 MPa.
  • the lower limit is more preferably 30 MPa.
  • the upper limit is more preferably 150 MPa.
  • the toughness can be set to 50 to 700 MJm- 3 .
  • the lower limit is more preferably 80 MJm -3 .
  • the upper limit is more preferably 500 MJm -3 .
  • the polymer of the present invention is preferable in that it can be made into a resin with excellent physical properties. Furthermore, these values are values obtained by the measurement method in the example of embodiment 1 in the examples of this specification.
  • the present invention may be a polymer consisting of only the above-mentioned polycaprolactone structure and components for forming a cyclodextrin skeleton in the side chain, but may also have other structural units.
  • the following specific examples of the use of other structural units in combination are the following aspects 1 and 2.
  • the polymer of embodiment 1 is a polyurethane resin having a biodegradable aliphatic polyester skeleton, to which a structure derived from compound (A) has been introduced.
  • the resin chain penetrates the cyclodextrin ring to form a crosslinking point, and the crosslinking point by CD slides when stress is applied, resulting in a mobile crosslinked material that exhibits high stress dispersibility.
  • the polymer has a skeleton derived from a compound having two or more hydroxyl groups in a structure other than the cyclodextrin skeleton. Since such a compound (A) has a functional group that reacts with isocyanate, it can be introduced into the polymer by reacting it with a polyisocyanate compound.
  • An example of the chemical formula of a compound obtained by such a reaction is shown below.
  • the aliphatic polyester (B) is a polycaprolactone having a diethylene glycol skeleton in part
  • the isocyanate compound (C) is tetramethylene diisocyanate
  • a specific compound represented by the general formula (2) is used as the compound (A).
  • Such a compound is one example of the polymer of the present invention, and the present invention is not limited to such a specific polymer.
  • Compound (A) having a functional group reactive with two isocyanate groups present in the cyclodextrin skeleton and in a structure other than the cyclodextrin skeleton Compound (A) is a compound having a cyclodextrin ring.
  • a crosslinked structure is formed by the main chain derived from another component penetrating the cyclodextrin ring of such compound (A).
  • Compound (A) has a cyclodextrin skeleton represented by the above general formula (1), and further has two or more functional groups reactive with isocyanate groups.
  • functional groups reactive with isocyanate groups include hydroxyl groups, amino groups, and carboxyl groups. These functional groups react easily with polyisocyanate compounds. Therefore, they are incorporated into the resin through the reaction of each of the components (A) to (C) described in detail below. This results in a resin having a cyclodextrin structure in the side chain relative to the polymer main chain. The main chain penetrates through this cyclodextrin structure to form a crosslinked structure.
  • compound (A) it is necessary that there are two or more functional groups reactive with isocyanate groups. This allows compound (A) to be incorporated into the polymer main chain, resulting in a polymer having a cyclodextrin structure in the polymer side chain. When there are two functional groups reactive with isocyanate groups, a chain resin is obtained. When there are three or more functional groups reactive with isocyanate groups, such a compound itself becomes a crosslinking point. It is particularly preferable to use a compound with a total of two functional groups reactive with isocyanate groups, as this makes it easier to control the physical properties and easier to handle.
  • Such compounds include those having the following structures in the molecule: It is preferred that the compound has a structure represented by the following formula: Compounds having such structures are preferable in that they can be easily synthesized and produced from relatively inexpensive raw materials.
  • Such compounds can be obtained, for example, by reacting a compound having an unsaturated bond and a cyclodextrin structure with ⁇ -thioglycerol. In other words, they can be obtained by adding ⁇ -thioglycerol to the unsaturated bond. Therefore, any compound having an unsaturated bond and a cyclodextrin structure can be converted into such a compound.
  • R 1 is the same or different and represents a hydrogen atom, an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 (R 2 is an alkyl group having 1 to 20 carbon atoms), and 20% or more of R 2 are any one of an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 3 .
  • R3 is an alkyl chain having 1 to 20 carbon atoms which may have an amide group, an ester group or a sulfide group in the main chain.
  • X 1 and X 2 are the same or different and each represents OH or NH 2
  • x is an integer of 5 to 7.
  • R 1 is (A) The following general formula (12): -R 3 -NH-R 4 (12) ( R3 is an alkylene group having 3 to 20 carbon atoms, which may be linear or branched, and may have a substituent.
  • R4 is a structure represented by the following formula: In the formula, R 10 represents hydrogen or a methyl group.
  • R6 is the same as R4 above.
  • R5 and R6 are the same as above.
  • R2 represents a hydrogen atom, an acyl group having 2 to 50 carbon atoms, or an alkyl group having 1 to 30 carbon atoms.
  • Rc represents a group represented by the following general formula (1).
  • R 1 's may be the same or different and represent an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 (R 2 is an alkyl group having 1 to 20 carbon atoms), and 20% or more of R 1's are any one of an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 .
  • x is an integer from 5 to 7 More specifically, such compounds include
  • R 1 is the same or different and represents a hydrogen atom, an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 (R 2 is an alkyl group having 1 to 20 carbon atoms), and R 7 represents a hydrogen atom or a methyl group.
  • R 8 is an alkylene chain having 2 to 20 carbon atoms. Examples include:
  • Such a compound is preferable because it is relatively easy to synthesize and can have a high purity.Furthermore, the obtained polymer is preferable because it has a high degree of freedom and can be designed so that the main chain can easily penetrate because the distance between the main chain and the cyclodextrin can be appropriately controlled.
  • Such compounds are particularly suitable for use in the present invention.
  • the resulting polymer has particularly excellent physical properties.
  • Such compounds can be obtained by reacting a compound having an unsaturated group described in WO 2022/024908 with ⁇ -thioglycerol.
  • the main chain skeleton has a structural unit based on the aliphatic polyester (B).
  • Aliphatic polyesters are known as resins having biodegradability, and by using them as a main structural unit, a polymer with low environmental impact can be obtained.
  • Examples of the aliphatic polyester resin (B) that can be used in embodiment 1 include those mentioned above.
  • the aliphatic polyester (B) as a structural unit preferably has a number average molecular weight of 1,000 to 4,000.
  • the method for measuring the number average molecular weight is the method described in the Examples.
  • the polyisocyanate compound (C) is a well-known compound widely known in the field of resins, and any of these can be used.
  • the polyisocyanate compound (C) is preferably a diisocyanate.
  • a crosslinked structure based on a multifunctional structure having three or more functional groups is not necessary.
  • a crosslinked structure based on a polyfunctional structure having three or more functional groups may be used. Even when a tri- or higher functional polyisocyanate compound is partially used, the amount used is preferably 15.0 mass % or less based on the total amount of the polyisocyanate compounds.
  • Diisocyanates include, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, (o-, m- or p-)xylene diisocyanate, methylene bis(cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene isocyanate, 1,5-naphthalene diisocyanate, and norbornane diisocyanate.
  • the amount of the compound (A) is preferably 0.1 to 10% by weight based on the total amount of the compounds (A) to (C). By setting the amount within this range, the number of crosslinks in the polymer can be set within an appropriate range, which is preferable in that a polymer having required physical properties can be obtained.
  • the lower limit of the amount of compound (A) is more preferably 0.7% by weight.
  • the upper limit of the amount of compound (A) is more preferably 1.3% by weight, and even more preferably 1.0% by weight.
  • the amount of the compound (B) is preferably 85.0 to 95.0% by weight based on the total amount of the compounds (A) to (C). By setting the amount within this range, the number of crosslinks in the polymer can be set within an appropriate range, which is preferable in that a polymer having required physical properties can be obtained.
  • the lower limit of the amount of compound (B) is more preferably 8.0% by weight.
  • the upper limit of the amount of compound (B) is more preferably 93.0% by weight, and even more preferably 90.0% by weight.
  • the amount of the compound (C) is preferably 1 to 10% by weight based on the total amount of the compounds (A) to (C). By setting the amount within this range, the number of crosslinks in the polymer can be set within an appropriate range, which is preferable in that a polymer having required physical properties can be obtained.
  • the lower limit of the amount of compound (C) is more preferably 1.5% by weight.
  • the upper limit of the amount of compound (C) is more preferably 3.0% by weight, and even more preferably 4.8% by weight.
  • the polymer of the present invention has the above-mentioned components (A) to (C) as structural units.
  • Such a polymer can be obtained by mixing the above-mentioned components (A) to (C) in an organic solvent solution and heating the mixture to 40 to 80°C.
  • a catalyst may be used.
  • the catalyst is not particularly limited, and examples thereof include N,N-dimethylcyclohexylamine, dibutyltin dilaurate, N-ethylmorpholine, bis(2,dimethylaminoethyl)ether, 2,2'-oxybis(N,N-dimethylethylamine), triethanolamine, etc.
  • the polymer of aspect 1 of the present invention has the above-mentioned chemical structure, and in particular, it is preferable that the polymer has the following physical properties. By satisfying the following properties, the polymer can be made to have more suitably excellent physical properties.
  • the polymer of the present invention preferably has a number average molecular weight of 10.0 to 65.0 kDa.
  • the polymer of the present invention preferably has a weight average molecular weight of 15.0 to 100 kDa. The molecular weight is measured according to the method described in the Examples.
  • the polymer of the present invention preferably has a glass transition temperature of ⁇ 50.0° C. to ⁇ 60.0° C.
  • the glass transition temperature is measured according to the method described in the Examples.
  • the polymer of the present invention preferably has a melting point of 40.0° C. to 45.0° C.
  • the melting point is measured according to the method described in the Examples.
  • the polymer of the present invention can be molded into a desired shape by applying a solution of the polymer onto a substrate and drying it, although the molding method is not particularly limited.
  • the polymer of the present invention can also be molded by hot press molding.
  • the polymer of embodiment 2 is obtained by polymerizing ⁇ -caprolactone (the polymer obtained by this polymerization reaction may be referred to as the second polymer) in the presence of an acrylic polymer (C) having a cyclodextrin skeleton as a side chain of the polymer (hereinafter, this may be referred to as the first polymer).
  • the first polymer and the second polymer form a structure called an interpenetrating structure, in which they are closely entangled, and this improves the physical properties.
  • a first polymer having a cyclodextrin skeleton is used. Since such a first polymer has a crosslinked structure in which the main chain penetrates the cyclodextrin ring, an interpenetrating structure is more suitably formed. It is also presumed that a portion of the polycaprolactone structure penetrates the cyclodextrin ring.
  • the polymer of the present invention has physical properties that are significantly different from those of a resin mixture obtained by blending the acrylic polymer (C) with polycaprolactone, and has unique and excellent physical properties that cannot be obtained by simply blending.
  • the acrylic polymer having a cyclodextrin ring in the side chain may be a known polymer, and may be, but is not limited to, a copolymer of a monomer having a cyclodextrin ring in the side chain and another unsaturated polymer.
  • the monomer having a cyclodextrin ring in the side chain is not particularly limited, and examples thereof include known monomers. Specific examples thereof include monomers described in International Publication No. 2012/036069 and International Publication No. 2022/024908.
  • radical polymerizable monomers include those represented by the following general formula (a1):
  • Ra represents a hydrogen atom or a methyl group
  • R3 represents a halogen atom, a hydroxyl group, a thiol group, an amino group or a salt thereof which may have one substituent, a carboxyl group or a salt thereof which may have one substituent, an amide group or a salt thereof which may have one or more substituents, or a phenyl group which may have one or more substituents.
  • Examples of the compound include compounds represented by the following formula:
  • R 3 when R 3 is a carboxyl group having one substituent, examples of the carboxyl group include carboxyl groups (i.e., esters) in which the hydrogen atom of the carboxyl group is substituted with a hydrocarbon group, methoxypolyethylene glycol (the number of ethylene glycol units is 1 to 20, preferably 1 to 10, particularly preferably 2 to 5), ethoxypolyethylene glycol (the number of ethylene glycol units is 1 to 20, preferably 1 to 10, particularly preferably 2 to 5), etc.
  • carboxyl groups i.e., esters
  • methoxypolyethylene glycol the number of ethylene glycol units is 1 to 20, preferably 1 to 10, particularly preferably 2 to 5
  • ethoxypolyethylene glycol the number of ethylene glycol units is 1 to 20, preferably 1 to 10, particularly preferably 2 to 5
  • R3 is an amide group having one or more substituents, that is, a secondary amide or a tertiary amide
  • examples of the amide group include an amide group in which one hydrogen atom or two hydrogen atoms of the primary amide are each independently substituted with a hydrocarbon group or a hydroxyalkyl group (for example, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group).
  • R 3 is preferably a carboxyl group in which a hydrogen atom is substituted with an alkyl group having 1 to 10 carbon atoms, or an amide group in which one or more hydrogen atoms are substituted with an alkyl group having 1 to 10 carbon atoms.
  • the other radical polymerizable monomer is relatively highly hydrophobic, and copolymerization with the host group polymerizable monomer is likely to proceed.
  • the alkyl group as the substituent has 2 to 8 carbon atoms, particularly preferably 2 to 6 carbon atoms, and in this case, the toughness and strength of the obtained polymer material are also likely to be improved.
  • This alkyl group may be either linear or branched.
  • monomers represented by formula (a1) include (meth)acrylic acid, allylamine, maleic anhydride, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, N,N-dimethyl (meth)acrylamide, N,N-diethylacrylamide, N-isopropyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylamide, ethoxy-diethylene glycol acrylate, methoxy-triethylene glycol acrylate, methoxy-polyethylene glycol acrylate, and
  • the structural units derived from the monomer having a cyclodextrin ring in the side chain described above are contained in a proportion of 5 to 70% by mass of the entire polymer. By keeping it within this range, it is preferable in that the effect of improving physical properties is significantly obtained.
  • the lower limit is more preferably 10% by mass, and even more preferably 15% by mass.
  • the upper limit is more preferably 65% by mass, and even more preferably 60% by mass.
  • the polymerization method for the polymer constituting the copolymer or resin composition of the present invention is not particularly limited, and can be carried out by a general method. Specific examples include radical polymerization by heat, radical polymerization by light, anionic polymerization, cationic polymerization, etc. Among these, radical polymerization is particularly preferred.
  • the above-mentioned photopolymerization initiator is not particularly limited, and examples thereof include acetophenone-based initiators such as 1-hydroxycyclohexyl phenyl ketone (trade name: IRGACURE 184), 2-hydroxy-2-methylpropiophenone (trade name: IRGACURE 1173), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one; benzoin-based initiators such as benzoin and 2,2-dimethoxy-1,2-diphenylethane-1-one; benzophenone, [4-(methylphenylthio)phenyl]phenylmethanone, 4-hydroxybenzophenone, and 4-phenylbenzophenone.
  • acetophenone-based initiators such as 1-hydroxycyclohexyl phenyl ketone (trade name: IRGACURE 184), 2-
  • Benzophenone-based initiators such as 2-chlorothioxanthone and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone-based initiators such as 2-chlorothioxanthone and 2,4-diethylthioxanthone; acylphosphine oxide-based initiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; and oxime ester-based initiators such as 1,2-octanedione, 1-[4-(phenylthio)phenyl], 2-(0-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazoyl-3-yl]-, and 1-(0-acetyloxime).
  • the amount of the photopolymerization initiator used
  • the conditions for photopolymerization are not particularly limited, and light sources include high-pressure mercury lamps, LED lamps, metal halide lamps, etc.
  • the radical polymerization initiator is not particularly limited, and azobisisobutyronitrile (AIBN), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2-methylpropionate)dimethyl, 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide, etc. are usable.
  • the amount of the thermal polymerization initiator used is preferably 0.1 to 2% by weight based on the total amount of monomers constituting the copolymer or resin composition of the present invention.
  • the polymer of the present invention is obtained by polymerization of ⁇ -caprolactone in the presence of the above-mentioned acrylic polymer (C).
  • the polymerization of ⁇ -caprolactone can be carried out by dissolving the raw material ⁇ -caprolactone in an organic solvent solution of the acrylic polymer (C), by removing the solvent and impregnating the acrylic polymer (C) formed into a predetermined shape with a raw material such as ⁇ -caprolactone, by dissolving the acrylic polymer in ⁇ -caprolactone and polymerizing it, by heating the acrylic polymer to melt it, and then mixing it with ⁇ -caprolactone and polymerizing it in that state.
  • a part of the polycaprolactone may have a structural unit based on a diol compound represented by the general formula HO-R 3 -OH.
  • a diol compound represented by the general formula HO-R 3 -OH.
  • ethylene glycol diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, 1,4-benzenedimethanol, etc.
  • the amount used is preferably within the range of 0 to 1 mass% in terms of (diol compound)/(caprolactone+diol compound) (weight ratio). Using an amount within this range is particularly preferred in that suitable physical properties can be obtained.
  • the lower limit is more preferably 0.001 mass%, and even more preferably 0.01 mass%.
  • the upper limit is more preferably 0.5 mass%, and even more preferably 0.1 mass%.
  • a catalyst may be used in combination as necessary.
  • catalysts include tin(II) 2-ethylhexanoate, titanium(IV) tetrabutoxide, zinc bis(2-ethylhexanoate), calcium methoxide, tributyltin methoxide, zinc dibutoxide, and lipase.
  • the amount of catalyst is preferably 0.001 to 20% by mass.
  • the lower limit is more preferably 0.005% by mass, and even more preferably 0.01% by mass.
  • the upper limit is more preferably 0.5% by mass, and even more preferably 0.1% by mass.
  • polycaprolactone is preferably 20 to 90% by mass of the entire polymer. Within this range, the above-mentioned effects can be optimally exhibited.
  • the lower limit is more preferably 30% by mass, and even more preferably 40% by mass.
  • the upper limit is more preferably 80% by mass, and even more preferably 70% by mass.
  • the polymer of the second embodiment of the present invention has the above-mentioned chemical structure, and it is particularly preferable that the polymer has the following physical properties.
  • the polymer of the present invention preferably has a weight average molecular weight of 5,000 to 2,000,000. The molecular weight is measured according to the method described in the Examples. Specifically, the molecular weight is calculated by measuring the molecular weight by size exclusion chromatography. (Eluent: chloroform, standard sample: polystyrene) (Glass Transition Temperature)
  • the polymer of the present invention preferably has a glass transition temperature of ⁇ 150 to 150° C.
  • the glass transition temperature is determined from the temperature at which a baseline shift is observed in the first heating process (heating rate 10° C./min) by differential scanning calorimetry. (Melting Point)
  • the polymer of the present invention preferably has a melting point of 50 to 250° C. The melting point is determined from the temperature at which a melting peak is observed in the first heating process (heating rate 10 ° C./min) by differential scanning calorimetry.
  • the polymer of the present invention is not particularly limited in its applications, and can be used in molded products and adhesives for automobile parts, electrical appliances, agricultural materials, office supplies, daily necessities, etc.
  • TAc ⁇ CD-diOH (a compound represented by general formula (2)) was prepared according to the method described in Non-Patent Document 1.
  • ⁇ -Thioglycerol, hexamethylene diisocyanate (HDI), dibutyltin diacetate (DBTDA), N,N,N'-tetrakis(2-hydroxyethyl)ethylenediamine (THEED) were purchased from ⁇ -caprolactone ( ⁇ -CL), tin(II) bis(2-ethylhexanoate) (Sn(Oct)2), diethylene glycol from Wako Pure Chemical Industries, Ltd. Dry N,N-dimethylformamide (DMF), methanol (MeOH), dichloromethane (DCM), and chloroform-d were from Tokyo Chemical Industry Co., Ltd. Reagents and solvents were used without further purification.
  • NMR nuclear magnetic resonance
  • MALDI-TOF MS Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry
  • Tensile test Tensile tests of the polymers were performed using an Autograph AG-X plus (Shimadzu Corporation) at 25°C with a deformation rate of 1 mm/s. All samples were tested using at least three specimens to calculate the average values of the mechanical properties and their standard deviations. Young's modulus was calculated from the initial slope of the stress-strain curve in the range of 1-6% strain up to the yield point, and the curve showed a linear increase. The toughness value was calculated as the integral of the stress-strain curve from 0% strain to the fracture strain point. The geometry of the samples used is shown in Figure 45.
  • Cyclic Tensile Test Cyclic tensile tests were performed using an Autograph AG-X plus (Shimadzu Corporation). The specimens were continuously stretched and recovered without intervals, and the maximum strain was set to 200% for 10 times at a deformation rate of 1 mm/s. Cyclic tensile tests at different maximum strains were set to 200%, 400%, 600%, 800%, 1000%, and 1200% at a deformation rate of 1 mm/s.
  • Stress Relaxation Test Stress relaxation tests were performed using an Autograph AG-X plus. (Shimadzu Corporation). The specimen was stretched to 800%. The strain was then held and the stress was recorded for 3600 seconds.
  • GPC Gel Permeation Chromatography
  • the measurement was performed using a Tosoh HLC-8420GPC EcoSEC (registered trademark, Tosoh Corporation) and two Tosoh TSKgel columns (TSKgel G2500HHR and TSKgel G4000HHR) as columns.
  • DSC Differential Scanning Calorimetry: The glass transition temperature (Tg) and melting point (Tm) of the sample were measured by differential scanning calorimetry under N2 gas flow (20 mL/min). The equipment used was a Hitachi High-Technologies Corporation DSC 7020 system. Measurements were performed at 10°C/min in the temperature range from -100°C to 100°C. All samples were first cooled to -100°C and then heated to 100°C, and the curves at this stage are called the first scan. After cooling again to -100°C, all samples were heated again to 100°C, and the curves at this stage are called the second scan.
  • Tg glass transition temperature
  • Tm melting point
  • TGA Thermogravimetric analysis
  • ATR-FTIR Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was measured using a JASCO FT/IR-6100 spectrometer in the wavenumber range of 4000-800 cm -1 .
  • the mixture of TAc ⁇ CD-diOH and PCLx-diOH was heated at 80°C under vacuum overnight to remove moisture.
  • the mixture of TAc ⁇ CD-diOH (a mol%) and PCLx-diOH ((100-a) mol%) was sonicated at 60°C for 30 minutes and then dissolved in dry DMF.
  • the reaction mixture was heated at 60°C for 24 hours under N2 .
  • X 1.5k, 2.4k, 3.5k.
  • a mol% of TAc ⁇ CD-diOH.
  • Tg and ⁇ H obtained from DSC is shown in (a) crosslinking ratio/Tg and (b) crosslinking ratio/ ⁇ H. From these results, (a) when crosslinking points were introduced, all crosslinked polymers showed higher Tg than lPCL 2.4k -PU, and the higher the crosslinking amount, the higher the Tg. (b) It was revealed that ⁇ H increased by introducing the covalent bond crosslinker THEED, but ⁇ H decreased slightly by introducing the mobile crosslinker CD.
  • Recyclability test method After tensile testing, the samples were collected and dissolved in DCM at room temperature (25-30°C). The solution was poured into a Teflon mold. The film was obtained by leaving it at room temperature for 24 hours and then at 35°C overnight under vacuum. The toughness measured for the obtained film is shown in Figure 38.
  • the Mn of PCL3.5k- ⁇ CD(9)-PU changes little.
  • the Mn of PCL3.5k- ⁇ CD(9)-PU began to decrease after 1 hour and reached a minimum after 12 hours.
  • the Mn of PCL3.5k-PU without mobile crosslinks hardly changed.
  • the Mn of PCL3.5k- ⁇ CD(9)-PU continued to increase within 8 hours and then began to decrease.
  • the Mn of PCL3.5k- ⁇ CD(5)-PU continued to increase within 96 hours.
  • the Mn of lPCL3.5k-PU hardly changed even after 120 hours.
  • the results in these figures show that the PCL-PU exhibits higher elongation and breaking strength than the PCL-PU that does not contain cyclodextrin.
  • the fact that the PCL-PU exhibits high elongation and breaking strength even at a relatively small molar ratio of cyclodextrin makes it clear that the PCL-PU exhibits very high toughness as a result.
  • the physical properties differ depending on the difference in resin structure, and that by using these appropriately depending on the purpose, the polymer of the present invention can be used in a wide range of applications.
  • Ethyl acrylate (EA) (Tokyo Chemical Industry Co., Ltd.) (2) Acetylated ⁇ -cyclodextrin-acrylamide (Ac- ⁇ -CDAAm) (Yushiro Chemical Industry Co., Ltd., Kyoeisha Chemical Co., Ltd.) (3) 1-Hydroxycyclohexyl phenyl ketone (Irgacure 184) (Tokyo Chemical Industry Co., Ltd.) (4) ⁇ -caprolactone (CL) (Tokyo Chemical Industry Co., Ltd.) (5) Ethylene glycol (FUJIFILM Wako Pure Chemical Industries, Ltd.) (6) Tin 2-ethylhexyl ester II (Sn(Oct) 2 ) (FUJIFILM Wako Pure Chemical Industries, Ltd.) (7) Deuterochloroform (FUJIFILM Wako Pure Chemical Industries,
  • the MC elastomer with a network by mobile crosslinks was synthesized according to the method described in NPG Asi Mater., 2022, 14, 1.
  • EA (2.3 g, 23 mmol) was placed in a sample tube, and Ac- ⁇ -CDAAm (0.55 g, 0.23 mmol) and Irgacure 184 (9.6 mg, 0.047 mmol) were dissolved therein.
  • the solution was then stirred for 60 minutes by ultrasonic vibration.
  • the solution was transferred to a mold and reacted by irradiating with ultraviolet light for 30 minutes while cooling with ice.
  • the resulting elastomer was transferred to a Teflon (registered trademark) petri dish and dried under reduced pressure at 80°C for 12 hours in a vacuum heat dryer to remove unreacted monomers.
  • MC elastomers were prepared with varying amounts of Ac- ⁇ -CDAAm introduced, 1.0, 2.0, and 3.0 mol%, as shown in Table 7 below.
  • a colorless and transparent elastomer was obtained by synthesizing MC elastomer.
  • 1H NMR measurement using deuterated chloroform as a solvent showed that the MC elastomer had characteristic peaks derived from the acetyl group of Ac- ⁇ -CDAAm, and the peaks derived from the vinyl group had disappeared, confirming that the synthesis of the MC elastomer had progressed.
  • the introduction rate of ⁇ -CD was 0.88% for pEA ⁇ CD_1 and 2.0% for pEA ⁇ CD_2.
  • Example 2 ⁇ -caprolactone (1.1 g, 1 mL) was placed in a sample tube, and Sn(Oct) 2 (0.18 g, 0.44 mmol) was dissolved therein to prepare a catalyst solution.
  • Caprolactone 5.4 g, 5 mL was also placed in a sample tube, and ethylene glycol (0.17 g, 2.7 mmol) was added thereto to prepare an initiator solution.
  • ⁇ -caprolactone (0.60 g) was placed in a ground test tube, and 12 ⁇ L each of the catalyst solution and initiator solution were added thereto and stirred.
  • MC elastomer (0.60 g) was added thereto and stirred well to swell the MC elastomer with the solution.
  • test tube was sealed with a silicon septum and the inside was replaced with nitrogen.
  • the test tube was then heated at 110 oC for 48 hours to polymerize CL and introduce PCL polymer chains into the MC elastomer.
  • the type of MC elastomer and the amount of PCL introduced were changed to prepare samples as follows.
  • Size exclusion chromatography was used to analyze the molecular weight of the introduced polycaprolactone. Chloroform was used as the mobile phase, and polystyrene as the standard sample. A single elution peak appeared for the MC elastomer, whereas a new peak appeared on the low molecular weight side for the mobile cross-linked network material. Comparing the two, the peak on the low molecular weight side is considered to be the elution peak of the introduced PCL ( Figure 48). In the material prepared using pEA ⁇ CD_1, the number average molecular weight of PCL was approximately 10,000. On the other hand, a decrease in the molecular weight of PCL was observed with pEA ⁇ CD_3. This is thought to be the result of the increase in the number of cross-linking points as the amount of ⁇ -CD introduced increases, causing the network structure of the MC elastomer to become denser, inhibiting the polymerization of CL (Table 9).
  • pEA ⁇ CD1_PCL50 prepared by in situ polymerization with pEA ⁇ CD1_PCL50_M prepared by simple mixing
  • pEA ⁇ CD1_PCL50 was a homogeneous material with high transparency
  • pEA ⁇ CD1_PCL50_M was a material with a non-uniform appearance. This is thought to be because pEA ⁇ CD1_PCL50 forms a dense network in which the polymer chains of polycaprolactone penetrate into a mobile crosslinked network of MC elastomer, whereas pEA ⁇ CD1_PCL50_M forms less of such a network.
  • the prepared MC elastomer and materials were molded into a film having a thickness of about 300 ⁇ m by heat pressing.
  • the heat pressing was performed as shown in Figure 44, with a pressure of 20 MPa and a temperature of 80° C. After the heat pressing, the sample was cooled on ice.
  • the mechanical properties of the MC elastomer and the prepared mobile crosslinked network material were evaluated by tensile tests.
  • the film-shaped sample was cut with a cutter to prepare test pieces as shown in Figure 45.
  • the tensile tests were performed using a 10 N load cell at a tensile speed of 10 mm per minute.
  • Figure 49 shows the results of tensile tests on MC elastomer and mobile cross-linked network material. As the amount of ⁇ -CD introduced increased, the breaking strain of the MC elastomer decreased and the maximum stress tended to increase (Figure 49a). This is thought to be due to the effect of increased cross-link density in addition to the molecular rigidity of ⁇ -CD itself. 50 wt% polycaprolactone was introduced into the MC elastomer.
  • pEA ⁇ CD1_PCL50 Comparing the mechanical properties of pEA ⁇ CD1_PCL50, pEA ⁇ CD2_PCL50, and pEA ⁇ CD3_PCL50, pEA ⁇ CD1_PCL50 showed the highest values for both breaking strain and maximum stress.
  • pEA ⁇ CD1_PCL50 showed the greatest improvement in properties for both toughness and initial modulus. This is thought to be due to the effect of introducing PCL, a molecular chain with relatively high rigidity, into the network.
  • pEA ⁇ CD3_PCL50 showed improved toughness due to an increase in breaking strain (Figure 49b). This is thought to be due to the incorporation of polycaprolactone polymer chains into the network of pEA ⁇ CD_3, which has a high cross-linking density, expanding the network and improving the flexibility of the material.
  • the polymer of the present disclosure has a low environmental impact because it uses an aliphatic polyester resin, while having excellent physical properties, and therefore can be used in many fields where such performance is required.

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Abstract

L'invention fournit un polymère qui est biodégradable, et simultanément qui possède un squelette de résine de polyester aliphatique présentant d'excellentes performances en termes de résistance. Plus précisément, l'invention concerne un polymère qui possède un squelette de cyclodextrine en tant que chaîne latérale de polymère, et qui possède une structure de résine de polyester d'acide gras dans au moins une partie.
PCT/JP2024/017026 2023-05-08 2024-05-08 Polymère, et composé insaturé Pending WO2024232370A1 (fr)

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