WO2007026886A1 - Mélange de polymères à polyrotaxane et son utilisation - Google Patents

Mélange de polymères à polyrotaxane et son utilisation Download PDF

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WO2007026886A1
WO2007026886A1 PCT/JP2006/317363 JP2006317363W WO2007026886A1 WO 2007026886 A1 WO2007026886 A1 WO 2007026886A1 JP 2006317363 W JP2006317363 W JP 2006317363W WO 2007026886 A1 WO2007026886 A1 WO 2007026886A1
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component
polymer blend
polymer
taxane
group
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PCT/JP2006/317363
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Japanese (ja)
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Kohzo Ito
Jun Araki
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The University Of Tokyo
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
    • C08B37/0015—Inclusion compounds, i.e. host-guest compounds, e.g. polyrotaxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/16—Cyclodextrin; Derivatives thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/96—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides

Definitions

  • the present invention relates to a polymer blend of a novel polyortaxane and a molded article containing the polymer blend.
  • Polymouth taxanes are pseudo molecules in which the opening of a cyclic molecule (rotator) is pierced by a linear molecule (axis), and the cyclic molecule includes the linear molecule. Blocking groups are arranged at both ends of the polyrotaxane (both ends of the linear molecule) so that the cyclic molecule is not released.
  • ⁇ -cyclodextrin as a cyclic molecule hereinafter, cyclodextrin may be simply abbreviated as “CD”) and polyethylene glycol as a linear molecule (hereinafter sometimes abbreviated as “PEG”) (See, for example, Patent Document 1), and these have been actively applied in recent years.
  • Patent Document 1 Japanese Patent No. 2810264
  • Non-patent literature l Harada, A .; Li, J .; Kamachi, M. Macromolecules 1990, 23, 2821-2823
  • Non-patent literature 2 Harada, A .; Li, J .; Kamachi, M. Nature 1992, 356,325 -327
  • Non-Patent Document 3 Harada, A .; Li, J .; Kamachi, M. Nature 1993, 364, 516-518 Disclosure of the Invention
  • An object of the present invention is to provide a polymer blend that is a polymouth taxane and other polymer materials. It is to provide and to provide a molded article comprising this polymer blend. Means for solving the problem
  • tertiary amine oxides or their hydrates, amides and halogenated metals, and ionic liquids are good solvents for polyoral taxanes, and other polymeric materials and polymers that can be dissolved therein.
  • tertiary amine oxides or their hydrates, amides and halogenated metals, and ionic liquids are good solvents for polyoral taxanes, and other polymeric materials and polymers that can be dissolved therein.
  • the present invention is selected from the group consisting of (1) a polyoral taxane, and (2) (a) a tertiary amine oxide or a hydrate thereof; an amide and a halogenated metal; and an ionic liquid force.
  • the present invention relates to a polymer blend that also has a polymer material power that can be dissolved in at least one solvent.
  • the present invention also relates to a molded article such as a fiber or film containing the polymer blend. The invention's effect
  • polypolytaxane and other polymer material strength properties derived from the polymouthtaxane (strength, elasticity, water absorption or (E.g., growth) can be newly added, and the utility value is high.
  • properties derived from the polymouthtaxane can be newly added, and the utility value is high.
  • the above-mentioned properties can be remarkably improved by crosslinking the poly (taxane) taxane.
  • crosslinking the poly (taxane) taxane By using this, it becomes possible to obtain a material having unprecedented physical properties.
  • the polyblend taxane of the present invention and other polymer blends having high polymer materials can be easily formed into molded articles such as fibers and films, and are highly useful.
  • FIG. 1 is a photomicrograph of fibers obtained using a solution containing a poly (taxane) taxane prepared from the solution (1) and the solution (2) of Example 3 at a volume ratio of 1: 2.
  • the polyortaxane refers to a quasi-polyrotaxane in which openings of a cyclic molecule are pierced by linear molecules and the cyclic molecules include the linear molecules (both linear molecules).
  • a linear molecule is a molecule or substance that is included in a cyclic molecule and can be integrated non-covalently, and is not particularly limited as long as it is linear. Any molecule, including molecules, may be used.
  • linear of “linear molecule” means substantially “linear”. That is, the linear molecule may have a branched chain as long as the cyclic molecule as a rotor is rotatable or the cyclic molecule is slidable or movable on the linear molecule. Further, the length of the “linear” is not particularly limited as long as the cyclic molecule can slide or move on the linear molecule.
  • the “straight chain” of the “linear molecule” is relatively determined depending on the relationship with the polymouth taxane material.
  • the linear molecule may be only a part in the material. Even if it is only a small part, the length is not particularly limited as long as the cyclic molecule can slide or move on the linear molecule as described above.
  • both a hydrophilic polymer and a hydrophobic polymer can be used.
  • the hydrophilic polymer include polybutanol, polypyrrole pyrrolidone, poly (meth) acrylic acid, cellulose-based resin (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc.), polyacrylamide, polyethyleneoxide, polyethylene.
  • Examples include glycols, polybulacetal resin, polybulumethyl ether, polyamines, polyethyleneimine, casein, gelatin, starch, and Z or copolymers thereof;
  • examples of hydrophobic polymers include Polyolefin, polypropylene, and other polyolefin resins such as copolymer resins, polyester resins, polychlorinated butadiene resins, polystyrene and acrylonitrile-styrene copolymers such as styrene copolymer resins
  • Acrylic resins such as tyrene-based resin, polymethylmetatalylate, (meth) acrylate copolymer, acrylonitrile methyl acrylate copolymer resin, polycarbonate resin, polyurethane resin, salt resin Examples thereof include vinyl copolymer resin, polyvinyl butyral resin, etc .; and derivatives or modified products thereof.
  • Polysiloxanes such as polysulfones, polysulfines, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and derivatives thereof should also be used Can do.
  • polyethylene glycol polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene are preferable. Particularly preferred is polyethylene glycol.
  • the linear molecule should have a number average molecular weight of 1,000 or more, for example, 1,000-1, 000, 000. More preferably, 5,000 or more, 5,000 to 1,000,000 or 5,000 to 500,000, even more preferable ⁇ is 10,000 or more, for example, 10,000 to 1,000,000 10,000 to 500,000 or 10,000 to 300,000.
  • the linear molecule preferably has reactive groups at both ends. By having a reactive group, it can easily react with a blocking group. Examples of reactive groups include forces that depend on the block group used, such as hydroxyl groups, amino groups, carboxyl groups, and thiol groups.
  • Examples of the cyclic molecule include various cyclodextrins, for example, unmodified cyclodextrins such as ⁇ -cyclodextrin, ⁇ -cyclodextrin, and ⁇ -cyclodextrin.
  • unmodified cyclodextrins such as ⁇ -cyclodextrin, ⁇ -cyclodextrin, and ⁇ -cyclodextrin.
  • a polyoral taxane whose cyclic molecule is a cyclodextrin is particularly insoluble and has few good solvents. This insolubility is thought to be because the hydroxyl groups present on the cyclodextrin form intramolecular and intermolecular hydrogen bonds, but the detailed mechanism is unknown.
  • cyclodextrins are dimethyl cyclodextrins, hydroxypropyl cyclodextrins, hydroxyethyl cyclodextrin, acetyl cycloalkyl cyclodextrins, etc., which have partially modified hydroxyl groups.
  • the above cyclodextrins have different sizes of the opening of the cyclic molecule depending on the type. Therefore, the type of linear molecule to be used, specifically, when the linear molecule to be used is assumed to be cylindrical, the cyclic molecule to be used depends on the diameter of the cross section of the cylinder, the hydrophobicity or hydrophilicity of the linear molecule, etc. Can be selected. Also, cyclic molecules with relatively large openings When using a cylindrical linear molecule with a relatively small diameter,
  • Two or more linear molecules can be included.
  • the blocking group is not particularly limited as long as it is a group that retains a form in which a cyclic molecule is skewered by a linear molecule, and any group may be used.
  • examples of such a group include a group having “bulkiness” and a group having Z or “ionicity”.
  • the “group” means various groups including a molecular group and a polymer group. That is, the group having “bulkyness” may be a group that is schematically represented by a sphere or a solid support represented by a side wall.
  • the “ionicity” of the group having “ionicity” and the “ionicity” of the cyclic molecule influence each other, for example, by repulsion, the cyclic molecule is skewered by a linear molecule. It is possible to retain the form.
  • the blocking group may be a polymer main chain or a side chain as long as it retains a skewered shape as described above.
  • the blocking group is polymer A
  • a form in which polymer A is partially contained may be used.
  • a composite material having a combination of the properties of the polymouth taxane material and the properties of the polymer A can be formed.
  • Examples of the blocking group include 2,4-dinitrophenyl group, 3,5-dinitrophenyl group and other di-trophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, and pyrene. And derivatives or modified products thereof.
  • cyclodextrin 2, 4-di-trifluoro group as a blocking group
  • di-trifluoro groups such as 3,5-di-phenol groups, adamantane groups, trityl groups, fluoresceins and pyrenes, and derivatives or modified products thereof.
  • the amount of the cyclic molecule penetrating in a straight chain molecule it is preferable to control the amount of the cyclic molecule penetrating in a straight chain molecule. It is preferable that at least two cyclic molecules are pierced with linear molecules, and at least two cyclic molecules include the linear molecules. In addition, the ring segment When the maximum amount of a molecule can be present on a linear molecule, that is, when the maximum inclusion amount is 1, the amount of cyclic molecules is 0.001 to 0.6, preferably the maximum inclusion amount. It is preferably present at a value of 0.01 to 0.5, more preferably 0.05 to 0.4.
  • polypolytaxanes have cyclodextrins, in particular (X-cyclodextrinca, pseudopolyrotaxane clathrating polyethylene glycol with blocking groups (adamantane groups, ditophole groups, etc.). Polymouth taxane.
  • the component (2) is a polymer material that can be dissolved in at least one solvent selected from the group consisting of (a) tertiary amine oxides or hydrates thereof; amides and halogenated metals; and ionic liquid forces. is there.
  • the polymer material does not contain the component (1).
  • the component (a) is a solvent that can also dissolve the component (1), and can function as a common solvent for the components (1) and (2).
  • the component (a) is a solid at room temperature, but includes those that exhibit fluidity by heating, preferably 40 to 150 ° C., and can function as a solvent. Specific examples are shown below.
  • Tertiary amine oxides or hydrates include N-methylmorpholine-N-oxide, N, N dimethylethanolamine-N oxide, N, N dimethylcyclohexylamine-N oxide, N, N, N Examples thereof include triethylamine-N oxide, N, N-dimethylbenzylamine N oxide, N-methylbiperidine N oxide, and the hydrates thereof.
  • N-methylmorpholine N-oxide monohydrate is preferred. These can be used alone or in combination of two or more.
  • Amides include formamide, ⁇ -methylformamide, ⁇ , ⁇ ⁇ ⁇ dimethylformamide, ⁇ , ⁇ jetylamide, acetoamide, ⁇ -methylacetamide, ⁇ , ⁇ dimethylacetamide, ⁇ -methyl-2-pyrrolidone, 1,3 dimethyl-2 And imidazolidinone.
  • ⁇ , ⁇ ⁇ ⁇ ⁇ dimethylacetamide, ⁇ -methyl-2 pyrrolidone, 1,3 dimethyl-2-imidazolidinone are preferred. These can be used alone or in combination of two or more.
  • the metal halide include alkali metal halides and alkaline earth metal halides.
  • halogen-alkali metal examples include lithium bromide, lithium chloride, potassium chloride, potassium bromide or hydrates thereof.
  • halogen-alkali earth metal examples include salt calcium, magnesium chloride, Forces such as calcium bromide and magnesium bromide are preferably lithium halides or hydrates thereof, and lithium chloride (anhydrous) is particularly preferable. These can be used alone or in combination of two or more.
  • a preferred combination of amide and metal halide is N, N-dimethylacetamide, N-methyl-2 pyrrolidone, 1,3 dimethyl-2 imidazolidinone or a mixture thereof and lithium chloride.
  • the metal halide is preferably 3 to 15% by weight, more preferably 5 to 12%, based on the total of the amide and the metal halide.
  • the ionic liquid has a melting point of 150 ° C. or less, a room temperature (about 25 ° C.), a vapor pressure of zero (or substantially zero), a high melting power and a wide range! ⁇ With a liquid range! ⁇ It shall mean an organic compound salt having characteristics.
  • the ionic liquids can be used alone or in combination of two or more.
  • the cation M + is selected from an ammonium compound, an imidazolium compound, a pyridinium compound, or a phosphonium compound, and is selected as an ion or a halogen ion). I prefer something that is.
  • the ammonium compound as the cation M + of the ionic liquid includes, for example, an aliphatic quaternary ammonium compound, specifically, tetraptyl ammonium, tetrapentyl ammonium. And tetraalkylammonium compounds such as Similarly, imidazolium compounds as cation M + include, for example, 1-ethyl-3-methylimidazole, 1-butyl-3-methylimidazole, 1-hexylo 3-methylimidazolium, 1 decyl-3-methylimidazolium. And N, N, -dialkyl imidazolium compounds such as 1-butyl-2,3 dimethylimidazolium.
  • pyridinium compounds include N-alkylpyridium compounds such as 1-hexylpyridium, 1-butyl-3 methylpyridium, and 1-butyl-4 methylpyridium.
  • Examples of the phosphonium compound as cation M + include tetraalkylphosphonium compounds such as tetrabutylphosphonium, triisobutylmethylphosphonium, and trihexyltetradecylphosphonium.
  • anion X— which is a counter ion of these compounds, a chloro ion is preferable.
  • Examples of the polymer material that can be dissolved in the component (a) include cellulose, chitin, chitosan, animal fibers, and synthetic polymers.
  • cellulose In particular, from the viewpoint of effective utilization of natural resources, cellulose, chitin, chitosan and animal fibers are preferred, and cellulose is particularly preferred.
  • the cellulose is not particularly limited, and a known cellulose can be used. Specific examples of cellulose include cotton, wood-derived pulp, bacterial cellulose, algae, and sea squirt-derived cellulose. Cellulose having an average degree of polymerization of 10 to 20,000 can be used, and particularly preferably 150 to 5,000. In the case of using pulp, the shape of the pulp, which uses both dissolved pulp and paper pulp, includes sheet, powder, and flock.
  • the cellulose includes derivatized cellulose.
  • Cellulose derivatives include cellulose ethers, cellulose esters, cellulose strength rubamates, and the like. Specifically, methyl cellulose, ethyl cellulose, propyl cellulose, cellulose diacetate, cenorelose triacetate, hydroxypropyl cellulose, hydroxy.
  • Chitin is a natural polysaccharide in which N-acetyl-D-darcosamine is 1,4- ⁇ linked. Chitin is not particularly limited, and known ones can be used.
  • chitin derived from shrimp, crustacean crustaceans, insect exoskeletons such as power beetles, fungal cell walls, algae and the like can be used.
  • Chitin having an average degree of polymerization of 10 to 10,000 can be used, and preferably 100 to 8,000.
  • Chitosan is a basic polysaccharide in which chitin is deacetylated.
  • Chitosan is not particularly limited, and known ones can be used. Specifically, chitosan having a degree of deacetylation of up to 95% can be used, preferably 30 to 70%. Further, chitosan having an average degree of polymerization of 10 to: LO, 000 can be used, and preferably 100 to 8,000.
  • animal fibers include silk fiber mouth-in and wool, but are not limited thereto.
  • synthetic polymer various synthetic polymers such as polyethers, polyols, and polyesters can be used.
  • Polyvinyl alcohol, polyacrylo-tolyl, polybutyropyrrolidone, polychlorinated bulu, polybulu Examples include but are not limited to acetate.
  • the weight ratio of the component (1) and the component (2) in the polymer blend of the present invention can be appropriately changed according to the desired characteristics, application, and the like. From the point of change in properties due to blending, it is preferable that the weight ratio of component (1) to component (2) is 1:99 to 99: 1, more preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2.
  • the polymer blend of the present invention can generally be said to correspond to what is referred to as a compatible or miscible polymer blend, and comprises a (poly) polysaccharide containing (a) component, (1) component and (2) component. It can be prepared using a taxane-containing solution.
  • Examples of other components include an antioxidant. Specifically, gallic acid propylene, methyl gallate, ethyl gallate, gallic acid ester of isopropyl gallate; carbo-ro such as glyceraldehyde, L-ascorbic acid, isoscorbic acid, triose reductone, reductic acid, etc. Compound with adjacent double bond; ethylenediamine 4 Examples include acetic acid; inorganic salts such as calcium pyrophosphate, calcium chloride, and ammonium salt. In particular, propyl gallate is preferred.
  • additives such as a colorant, a plasticizer, a fragrance, a cross-linking agent, a surface treatment agent, and a pH adjusting agent may be mentioned.
  • a solvent other than the component (a) may be blended in the polymouth taxane-containing solution.
  • the component (a) is other than an amide or a halogenated metal, the amides mentioned in the component (a) may be preferably blended! / ⁇ .
  • a solvent may be blended that can be uniformly mixed with the component (a) and does not dissolve both the component (1) and the component (2).
  • Non-solvents include water; mixed solvents of water and lower alcohols (methanol, n-propanol, isopropanol, butanol); aprotic organic solvents such as toluene and xylene. Water is particularly preferable.
  • the polyortaxane-containing solution is prepared by mixing (1) component, (a) component, (2) component, and optionally other components, and stirring (1) component and (2) component. It can be prepared by dissolving. Alternatively, the solution of the component (a) to which the component (1) is added may be prepared separately from the solution of the component (a) to which the component (2) is added, and then these solutions may be mixed. In this case, the component (a) to which the component (1) is added and the component (a) to which the component (2) is added may be the same or different.
  • the dissolution temperature is not particularly limited and can be selected from the range in which component (a) exhibits fluidity. From the viewpoint of suppressing the decomposition of the components, the temperature is preferably in the range of room temperature to about 100 ° C, for example, in the range of room temperature to about 70 ° C.
  • the sum of the components (1) and (2) is 95% by weight or less in the solution, and the productivity is 0.5 to 50% by weight.
  • the polymer blend can be prepared by agglomerating the components (1) and (2) from a solution containing a polymouth taxane.
  • the agglomeration method is not particularly limited, and a known method can be used.
  • a polymouth taxane-containing solution is formed and brought into contact with a coagulation liquid to remove the component (a) and (1 ) And (2) components can be agglomerated.
  • the coagulation liquid include the non-solvents described above.
  • the coagulation solution can be obtained by adding a pH adjuster such as acetic acid.
  • Molded articles containing polymer blends can also be prepared by known methods.
  • a method in which a polymouth taxane-containing solution is discharged from a spinning nozzle into a coagulation bath, aggregated in a filament form, and taken out from the bath as a fiber can be employed.
  • the polymouth taxane-containing solution may be discharged from a spinning nozzle into the air, and the formed filamentous solution stream may be put into a coagulating liquid bath to be agglomerated.
  • a casting method in which a polymouth taxane-containing solution is cast and then brought into contact with a coagulation liquid in the next step V to agglomerate to form a film. It can also be prepared as a blown film by the inflation method.
  • Poly mouth taxane (PR) is as follows, and equivalent products can be purchased from Advanced Soft Materials Co., Ltd.
  • the linear molecule is PEG with an average molecular weight of 35,000. It has an adamantane group via an amide bond at the end.
  • the monocyclic molecule is ⁇ -CD, and the number of CDs included is 90-: LOO (inclusion rate is about 22-25%).
  • Cellulose is microcrystalline cellulose manufactured by Whatman and trade name CF11.
  • N, N dimethylacetamide (DMAc) is an experimental grade reagent manufactured by Wako Pure Chemical Industries, Ltd.
  • a molecular sieve 4A (manufactured by Wako Pure Chemical Industries, Ltd.) is placed in advance and left for a day. The water is removed.
  • Anhydrous lithium chloride (LiCl) is an experimental grade reagent manufactured by Wako Pure Chemical Industries, which has been dried at 105 ° C for 2 hours or more in advance.
  • Example 1 Preparation of molded article containing polymer blend
  • Methylmorpholine-4-oxide hydrate (NMMO) 9.5 g was melted by heating to 90 ° C, and crushed PR 250 mg and propyl gallate (PG) 5 mg were added. Heated for minutes. Next, add 250 mg of cellulose and stir at 100 ° C for an additional hour. A slightly viscous brown solution was obtained.
  • NMMO Methylmorpholine-4-oxide hydrate
  • the solution obtained above was deaerated by placing it in a vacuum dryer at 105 ° C. under vacuum for 10 to 15 minutes. 5 ml of the solution was cast in a Teflon petri dish ( ⁇ 50 mm) at a high temperature and further maintained at 105 ° C. for 10 minutes, and then cooled to room temperature in a desiccator and solidified. The solidified sample was immersed in a mixed solvent of methanol Z water (75Z25, v / v) to elute NMMO and PG. Washing with the mixed solvent was repeated twice, followed by washing with ion-exchanged water to obtain a white turbid gel-like molded product.
  • Example 2 Preparation of a film containing a polymer blend
  • NMM018g was melted by heating to 90 ° C., and PRlg and cellulose lg were added. When stirring with a magnetic stirrer, these dissolved and a translucent viscous solution was obtained, but some remained undissolved at the bottom of the container.
  • the solution obtained above is cast into a glass plate and then washed with methanol Z water (75 Z25, v / v) to elute NMMO and agglomerate the polymer blend of PR and cellulose. A slightly white translucent gel-like film was obtained.
  • Example 3 Preparation of fiber containing polymer blend
  • the solution (1) and the solution (2) were mixed at a volume ratio of 1: 2 to obtain a solution containing a poly (taxane) taxane.
  • the solution containing the polymouth taxane was extruded with a syringe into a beaker filled with methanol as a coagulation bath, and the polymer blend was coagulated into filaments and precipitated on the bottom surface. This was wound up on a centrifuge tube, heated at 60 ° C. and dried to obtain a fiber having a thickness of about 180 / zm.
  • the solution (1) and the solution (2) were mixed at a volume ratio of 1: 1, 2: 1, respectively, polypolytaxane-containing solutions were obtained and spun by the same method as described above. A 180 m fiber was obtained.
  • Example 4 Preparation of fiber containing polymer blend and evaluation of physical properties
  • the solution (1) and the solution (2) were mixed so that the weight ratio of the polymouth taxane to cellulose was the ratio shown in Table 1 below to obtain a polymouth taxane-containing solution. Then, using these solutions, fibers of Examples 4-1 to 4-3 were obtained in the same manner as in Example 3 (thickness: about 180 m).
  • a solution containing a poly (taxane) taxan was obtained in the same manner as in the solution (2) except that the amount of poly (taxane) added was 10 g. Then, using this solution, a fiber of Comparative Example 2 containing only a polymouth taxane was obtained (thickness of about 90) in the same manner as in Example 3 (extruding was performed using a nozzle having a small diameter). / ⁇ ⁇ ).
  • the present invention provides a new material that can be formed into fibers and films.
  • the present invention expands the possibilities as a raw material for poly-oral taxanes, and in recent years, the shape and physical properties of molded products using natural products such as cellulose, chitin, chitosan, etc., which are also attracting attention as a resource exhaustion problem. Application to can be expected.

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Abstract

La présente invention concerne un mélange de polymères composé de polyrotaxane et d'une autre substance polymère ainsi qu'un article moulé contenant ledit mélange. L'invention concerne un mélange de polymères comprenant (1) du polyrotaxane et (2)(a) une substance polymère soluble dans au moins un solvant, choisie dans le groupe constitué par un oxyde d'amine tertiaire ou un hydrate de celui-ci ; un amide et un halogénure métallique ; et un liquide ionique. L'invention concerne en outre un article moulé contenant le mélange de polymères.
PCT/JP2006/317363 2005-09-02 2006-09-01 Mélange de polymères à polyrotaxane et son utilisation WO2007026886A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2005255130 2005-09-02
JP2005-255130 2005-09-02
JP2006-129178 2006-05-08
JP2006129178A JP2007092024A (ja) 2005-09-02 2006-05-08 ポリロタキサンのポリマーブレンド及びその使用

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