WO2007129681A1 - 形状記憶樹脂 - Google Patents
形状記憶樹脂 Download PDFInfo
- Publication number
- WO2007129681A1 WO2007129681A1 PCT/JP2007/059442 JP2007059442W WO2007129681A1 WO 2007129681 A1 WO2007129681 A1 WO 2007129681A1 JP 2007059442 W JP2007059442 W JP 2007059442W WO 2007129681 A1 WO2007129681 A1 WO 2007129681A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- shape
- shape memory
- network polymer
- sample
- epoxidized
- Prior art date
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 42
- 239000011347 resin Substances 0.000 title claims abstract description 42
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 64
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 47
- 239000002243 precursor Substances 0.000 claims abstract description 44
- 239000004593 Epoxy Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000002844 melting Methods 0.000 claims description 21
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- 239000000203 mixture Substances 0.000 claims description 21
- 230000009477 glass transition Effects 0.000 claims description 19
- 229920000647 polyepoxide Polymers 0.000 claims description 16
- 239000003822 epoxy resin Substances 0.000 claims description 15
- 239000004626 polylactic acid Substances 0.000 claims description 11
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 10
- 239000003549 soybean oil Substances 0.000 claims description 9
- 235000012424 soybean oil Nutrition 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 8
- 235000019198 oils Nutrition 0.000 claims description 8
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000944 linseed oil Substances 0.000 claims description 6
- 235000021388 linseed oil Nutrition 0.000 claims description 6
- 235000019482 Palm oil Nutrition 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002540 palm oil Substances 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229920001222 biopolymer Polymers 0.000 claims 1
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- 238000001723 curing Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000004809 Teflon Substances 0.000 description 8
- -1 glycidyl ester Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
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- 238000000113 differential scanning calorimetry Methods 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 4
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 4
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 4
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 235000003441 saturated fatty acids Nutrition 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
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- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- DJIHQRBJGCGSIR-UHFFFAOYSA-N 2-methylidene-1,3-dioxepane-4,7-dione Chemical compound C1(CCC(=O)OC(=C)O1)=O DJIHQRBJGCGSIR-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 235000021353 Lignoceric acid Nutrition 0.000 description 1
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- RSPISYXLHRIGJD-UHFFFAOYSA-N OOOO Chemical compound OOOO RSPISYXLHRIGJD-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- CXOFVDLJLONNDW-UHFFFAOYSA-N Phenytoin Chemical compound N1C(=O)NC(=O)C1(C=1C=CC=CC=1)C1=CC=CC=C1 CXOFVDLJLONNDW-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical class NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- RQBJDYBQTYEVEG-UHFFFAOYSA-N benzylphosphane Chemical class PCC1=CC=CC=C1 RQBJDYBQTYEVEG-UHFFFAOYSA-N 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 235000021588 free fatty acids Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008169 grapeseed oil Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
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- 150000002632 lipids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
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- 239000011368 organic material Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- 239000002383 tung oil Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C08G2280/00—Compositions for creating shape memory
Definitions
- the present invention relates to a shape memory resin and a method for producing the same.
- shape memory materials which are put into practical use in metals as well as polymers. For example, “easily dismantled screws” that can be easily disassembled by heating without screw threads, or “shape memory spoons” that have a handle that can be deformed into a shape that can be easily used by people with disabilities. .
- shape memory materials are put into practical use in metals as well as polymers. For example, “easily dismantled screws” that can be easily disassembled by heating without screw threads, or “shape memory spoons” that have a handle that can be deformed into a shape that can be easily used by people with disabilities. .
- it is applied to medical fields such as infusion needles and catheters.
- shape memory materials appear based on phase transformations due to changes in crystal structure and changes in the form of molecular motion.
- the shape memory material is fixed to a temporary form by programming the shape and restored to the original form by applying an external stimulus.
- it is necessary to design and develop freely programmable materials, which requires strict structural control of materials at the molecular level.
- Shape memory polymers exhibit their functions based on changes in the movement of polymer chains due to phase transitions, and phase transitions at melting and glass transition temperatures are often used.
- a shape memory polymer is composed of a switch part and a hard part, and a network structure is formed by fixing the phase transition phenomenon of the switch part with the hard part. It retains its form as a fee.
- a shape memory polymer As a shape memory polymer, a material whose hard part is a physical bridge, typically polyurethane, is frequently used because of its easy formability (Japanese Patent Laid-Open No. 2 0 0 4-3 0 0 3 6 8 No. publication, Japanese Laid-Open Patent Publication No. 2 005-3 2 5 3 3 6 publication, and International Publication No. 9 9 Z 4 2 5 2 8 pamphlet).
- the hard segment containing the urethane bond is the hard part, and the elastic modulus change at the glass transition temperature of the polyurethane soft segment is used in the shape program. It is advantageous to use the melting point as the phase transition because it is possible to obtain a large width and variation width.
- the hard part when the hard part is physical cross-linking, the polymer chain cannot be retained by melting the polymer. As a result, the glass transition temperature must be used. For this reason, it is difficult to cope with large deformation and rapid shape change.
- the hard part in the case of shape memory polymers using melting, the hard part is often chemically crosslinked, but chemically crosslinked gels have poor moldability and have not led to the development of practical materials.
- the conventional shape memory polymer has a switch part and a hard part in the same polymer molecule, and thus requires a detailed molecular design and a complicated synthesis operation. Disclosure of the invention
- a shape memory resin based on a molecular design different from the conventional type was developed by utilizing the phase transition of a thermoplastic polymer in a blend of a network polymer and a thermoplastic polymer.
- the present invention provides a shape memory resin comprising a network polymer and a thermoplastic polymer, wherein the thermoplastic polymer is compatible with the network polymer precursor and is dispersed in the network polymer.
- the present invention also provides a method for producing a shape memory resin, Dissolving a thermoplastic polymer in a network polymer precursor to obtain a mixture;
- thermoplastic polymer is compatible with the network polymer precursor.
- the network polymer precursor is an epoxy compound.
- the epoxy compound is at least one selected from the group consisting of an epoxidized oil and an epoxy resin.
- the epoxidized fat is at least one selected from the group consisting of epoxidized soybean oil, epoxidized linseed oil, and epoxidized palm oil
- the epoxy resin is bis Phenolic type A epoxy resin.
- thermoplastic polymer is at least one selected from the group consisting of poly-strength prolatatatone, poly-salt polybule, polylactic acid, and poly (butylene succinate).
- the glass transition temperature or melting point of the thermoplastic polymer has a temperature difference of at least 20 ° C. from the glass transition temperature of the network polymer.
- the shape memory resin of the present invention uses an amorphous network polymer as a matrix, and a thermoplastic polymer chain is fixed at a molecular level in the matrix. Therefore, the shape memory function can be expressed by using the macroscopic change of the phase transition polymer (that is, thermoplastic polymer) in the network as an output.
- the shape memory resin of the present invention dissolves a thermoplastic polymer in a network polymer precursor (for example, an epoxy compound), and can be heated. It can be produced by a very simple method of curing above the phase transition temperature of the plastic polymer. Therefore, it can be easily applied to a wide range of resin combinations.
- A is a ring-shaped sample deformed by applying heat to the flat plate sample. The shape (deformed shape) is shown, and B is a photograph showing the shape (recovered shape) of a flat plate sample that has been recovered by immersing the ring shape in hot water.
- ESO stands for epoxidized soybean oil
- PC L stands for poly-prolacton.
- Fig. 3 is a graph showing the relationship between strain and tensile stress in a uniaxial extension test for flat samples molded using various proportions of ESO / B P AEP // PCL.
- B PAE P represents bisphenol A diglycidyl ether.
- PBS stands for poly (butylene succinate).
- PVC stands for poly salty bulle.
- 0) is a photograph showing the shape in the process of shape recovery from a deformed shape to a formed shape of a helical sample formed using
- a shape memory resin is a resin that can be molded and deformed using a temperature operation by heat.
- deformation is applied at a temperature above the glass transition temperature (Tg) of the shape memory resin itself, below the melting temperature or below the decomposition temperature, and cooled to below the glass transition temperature while maintaining its shape.
- Tg glass transition temperature
- the shape memory resin of the present invention has a relatively large temperature difference from the Tg or melting point of the thermoplastic polymer (for example, a relatively low Tg) in a matrix polymer (ie, a network polymer).
- the shape memory function is developed using the phase transition at the Tg or melting point of the dispersed thermoplastic polymer.
- the network polymer is a polymer formed by crosslinking of a network polymer precursor, and has a three-dimensional network structure. Further, in the present invention, the network polymer precursor is obtained by crosslinking. A polymer that can form a network.
- Examples of the network polymer precursor used in the present invention include an epoxy compound, a phenol resin, an acrylic resin, an unsaturated polyester, a melamine resin, and a urea resin.
- the network polymer precursors may be used alone or in combination of two or more.
- an epoxy compound is preferably used because it is easy to handle and has good moldability.
- the epoxy compound used in the present invention is not particularly limited as long as it is an epoxy resin or an epoxidized product of triglyceride containing an unsaturated group (that is, epoxidized oil).
- epoxy resin examples include bisphenol A type epoxy resin (for example, bisphenol A diglycidyl ether), novolak type epoxy resin, and glycidyl ester type epoxy resin. These may be those sold for industrial use. Typical examples of such commercially available epoxy resins include various types of Epicoat®.
- Epoxidized oils and fats are not particularly limited as long as they are epoxidized products of resins mainly composed of triglycerides containing unsaturated fatty acids as fatty acid components.
- natural triglyceride epoxidized products can be mentioned.
- natural triglycerides include natural oils such as soybean oil, linseed oil, fish oil, sunflower oil, tung oil, castor oil, corn oil, rapeseed oil, sesame oil, olive oil, palm oil, and grape seed oil.
- fatty acid components in such fats and oils include saturated fatty acids and unsaturated fatty acids ranging from C4 butyric acid to C2-4 lignoceric acid.
- the main saturated fatty acids are palmitic acid and stearic acid.
- the unsaturated fatty acids are oleic acid, linoleic acid and linolenic acid.
- the triglycerides having a high degree of unsaturation are preferred, those having a low ratio of saturated fatty acids in the fatty acid component are preferred, and those containing many epoxy groups when formed into an epoxy compound.
- soybean oil eg, saturated fatty acid in fatty acid component is 20% or less
- linseed oil e.g., saturated fatty acid in fatty acid component is 50% or less
- examples of commercially available epoxidized oils and fats include Daicel Chemical Industries' epoxidized linseed oil (trade name: Daicock L 1 500), epoxidized soybean oil (trade name: Daicock S—300 K), Examples include epoxidized soybean oil from Kao Corporation (trade name: Kapox S-6).
- Natural fats and oils may contain a small amount of free fatty acids, complex lipids, unsaponified products, etc. in addition to the above triglycerides, and the content of components other than triglycerides is generally 5% by mass or less.
- the above epoxidized fat is obtained by epoxidizing the unsaturated portion of the unsaturated fatty acid of triglyceride, that is, by oxidative conversion of carbon-carbon double bond to 1,2-epoxide (oxylan).
- the ratio (epoxidation rate) at which the unsaturated portion is epoxidized is higher, and the epoxidation rate is preferably 50 to 100%. Preferably, it is 70 to 100%.
- the epoxidation rate is less than 50%, a network with a high crosslinking rate is not formed, and the shape of the shape memory resin molded product tends to be difficult to be maintained.
- deterioration of the shape memory resin may be promoted by oxidation reaction of the remaining double bonds.
- the above epoxy compounds may be used alone or in combination of two or more. From the viewpoint of easily dissolving the thermoplastic polymer, it is preferably liquid at room temperature.
- thermoplastic polymer used in the present invention is not particularly limited as long as it is compatible with the network polymer precursor, and is appropriately selected according to the network polymer precursor. Selected.
- “compatible” means that two or more kinds of substances have an affinity for each other to form a solution or a mixture. In the present invention, if a solution or admixture is formed to such an extent that it can be visually confirmed, it is said to be compatible.
- the thermoplastic polymer used in the present invention may be a crystalline polymer or an amorphous polymer) /.
- thermoplastic polymers examples include poly-force prolatatone, polyvinyl chloride, polylactic acid, polystyrene, attalyl resin, polysulfone, polyacetate butyl, polyphenylene oxide, polyethylene oxide, polypropylene alcohol, poly ( Hydroxyalkanoate), Poly (ethylene succinate), Poly (butylene succinate), Polycarbonate, Poly (oxytetraethylene), Polyethylene, Polypropylene, Polyethylene terephthalate (PET), Polypropylene terephthalate (PBT), Nylon Polyphenylene sulfide (PPS).
- the network polymer precursor is an epoxy compound
- it will have good compatibility with this network polymer precursor in terms of poly-force prolatatone, poly-salt bull, poly-lactic acid, and poly (butylene succinate). Is preferred.
- These thermoplastic polymers may be used alone or in combination of two or more.
- the thermoplastic polymer used in the present invention preferably has a higher molecular weight in terms of maintaining the shape of the molded product.
- the number average molecular weight (M n) force is preferably at least 10 00 0 0, more preferably at least 3 0 0 0 0, more preferably at least 5 0 0 0 0 possible.
- the upper limit on the molecular weight of the thermoplastic polymer is not particularly limited as long as it is compatible with the network polymer precursor used. Note that the suitable molecular weight of the thermoplastic polymer may vary depending on the type and mixing ratio of the network polymer precursor.
- the glass transition temperature (T g) or melting point of the thermoplastic polymer preferably has a temperature difference of at least 20 ° C. from the T g of the network polymer in that the molded shape and the deformed shape can be clearly controlled.
- T g glass transition temperature
- the glass transition temperature (T g) or melting point of the thermoplastic polymer preferably has a temperature difference of at least 20 ° C. from the T g of the network polymer in that the molded shape and the deformed shape can be clearly controlled.
- the mixing ratio of the network polymer precursor and the thermoplastic polymer varies depending on the type of the network polymer precursor and the thermoplastic polymer used.
- the mixing ratio of the network polymer precursor to the thermoplastic polymer is usually 10:90 to 90:10, preferably 20:80 to 80:20, more preferably 2 by mass ratio. 5: 7 5-7 5: 25. If the network polymer precursor is too much, the deformability tends to deteriorate, and if it is too little, the shape tends to be difficult to maintain.
- a curing agent ie, a crosslinker or catalyst
- the type and amount of the curing agent are appropriately selected by those skilled in the art depending on the type of the network polymer precursor.
- an acid catalyst is preferably used as a curing agent for ring-opening polymerization of an epoxy group in the epoxy compound.
- a heat latent acid catalyst does not function as a catalyst at a temperature below a predetermined temperature, and decomposes to produce an acid and exerts a catalytic action when the temperature exceeds a predetermined temperature.
- thermo latent catalyst for example, an epoxy compound and a thermoplastic polymer can be sufficiently mixed at room temperature, and then the temperature is raised to cause a polymerization reaction, thereby obtaining a shape memory resin having a uniform composition.
- a photo-curing catalyst as a glaze! It may be.
- the heat latent acid catalyst is, for example, “a new phase of photofunctional organic / polymer materials” (supervised by Kunihiro Kashimura, CMC Publishing Co., Ltd., 2002).
- Anion polymerization catalyst specifically, aromatic sulfonium salts (for example, benzylsulfonium salts), benzylammonium salts, benzylphosphonium salts, etc. It is done. If the temperature at which acid is generated by the decomposition of the heat-latent acid catalyst is too low, the crosslinking reaction starts before the thermosetting treatment, and it becomes difficult to form a uniform network polymer. If it is too high, the epoxy compound and the thermoplastic polymer are not formed.
- the heat latent acid catalyst preferably has a temperature at which an acid is generated by decomposition of 50 to 25 ° C., and particularly preferably 80 to: L 80 ° C.
- the preferred addition amount of the curing agent is 0.1 to 20 parts by mass, particularly preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the epoxy compound. It is. If the amount is less than 0.1 part by mass, the crosslinking reaction of the epoxy compound tends not to be sufficiently completed, and if the amount exceeds 20 parts by mass, the crosslinking tends to be uneven.
- the method for producing the shape memory resin of the present invention comprises a step of dissolving the thermoplastic polymer in the network polymer precursor to obtain a mixed solution; and adding a hardener to the mixed solution to obtain the network polymer precursor. A step of crosslinking.
- the process of mixing the network polymer precursor and the thermoplastic polymer is usually performed at room temperature. If necessary, heating may be performed, or mixing may be promoted by ultrasonic waves. Alternatively, volatile organic solvents may be added to facilitate mixing.
- the network polymer precursor is crosslinked and molded.
- the molding method used in the present invention is appropriately selected by those skilled in the art according to the kind and mixing ratio of the network polymer precursor and the thermoplastic polymer, the desired shape of the molded body, and the like. Examples include casting, injection molding and dip molding.
- the heat treatment conditions for crosslinking the network polymer precursor in the mixture are selected according to the type of curing agent used, but are preferably from 50 to 25 ° C (more preferably from 80 to 180 ° C). It is preferable to select within the range.
- the crosslinking reaction tends not to proceed sufficiently.
- the temperature exceeds 250 ° C the network polymer precursor is volatilized and decomposed, resulting in a good shape memory resin. There is a tendency to become unobtainable.
- the reaction time required for the heat treatment is not particularly limited, but is preferably about 10 minutes to 24 hours, and more preferably about 30 minutes to 4 hours. If the reaction time is less than 10 minutes, the crosslinking reaction tends not to be sufficiently completed. On the other hand, if it exceeds 24 hours, the shape memory resin tends to gradually decompose.
- the obtained shape memory resin molded body is heated to a temperature higher than the phase transition temperature of the thermoplastic polymer (ie, T g or melting point) to give a deformed shape (or temporary shape), and then rapidly cooled. Can be fixed to this deformed shape. The deformed shaped body is restored to its original shape by heating again above the phase transition temperature.
- T g or melting point the phase transition temperature of the thermoplastic polymer
- This mixed solution was poured into a 44 mm ⁇ 5 mm ⁇ 1 mm fluororesin mold and heat-treated at 150 ° C. for 2 hours to obtain a flat sample (molded shape) having a thickness of about 1 mm.
- the sample was subjected to differential scanning calorimetry (DSC) (SSC / 5200: Seiko Instrume nts).
- the obtained flat sample was heated to 80 ° C., wound around a glass rod having an outer peripheral length of 44 mm, and immediately cooled to room temperature to obtain an annular sample (deformed shape) (FIG. 1A). The distance between both ends of the annular sample was measured. Next, the annular sample was immersed in 90 ° C hot water to recover (Fig. 1B), and the distance between both ends in the longitudinal direction of the recovered shape was measured. This operation was repeated four more times. The results are shown in Table 1.
- the thickness of the obtained flat sample (molded shape) was about 1.2 mm. The results are summarized in Table 1.
- the thickness of the obtained flat sample (molded shape) was about 1.4 mm. The results are summarized in Table 1.
- Example 2 The same procedure as in Example 1 was performed except that 25 parts by mass of ESO and 75 parts by mass of PCL were used, and that DSC was not performed. The thickness of the obtained flat sample (molded shape) was about lmm. The results are shown in Table 2. Table 2
- Example 3 The same procedure as in Example 1 was performed except that 75 parts by mass of ESO and 25 parts by mass of PCL were used, and that DSC was not performed. The thickness of the obtained flat sample (molded shape) was about ⁇ 6 mm. The results are shown in Table 3. Table 3
- a helical sample was obtained in the same manner as in Example 6 above. This helical sample was placed on an 80 ° C hot plate and the shape change over time was observed. As soon as it was placed on the hot plate, the spiral winding started to loosen and recovered to a nearly flat shape in about 60 seconds.
- This ESOZPCL flat plate sample was stretched at 5.0 mm / 7 minutes using EZ Grah (SHIMADZU) as a measuring device and subjected to a uniaxial stretching test.
- EZ Grah SHIMADZU
- a uniaxial extension test was also conducted on a flat polyurethane synthesized from ester-based polyol optotolylene diisocyanate.
- Polyurethane was synthesized as follows: refined castor oil (Ito Oil Co., Ltd.) 4 parts by mass, tolylene 1,4-diisocyanate (Tokyo Chemical Industry Co., Ltd.) 1 part by mass, and 40 parts by mass of black mouth form was mixed and stirred at 40 ° C. for 4 hours. Next, the mixed solution was poured into a fluororesin mold and heated at 140 ° C. for 15 minutes to obtain polyurethane.
- refined castor oil Ito Oil Co., Ltd.
- tolylene 1,4-diisocyanate Tokyo Chemical Industry Co., Ltd.
- the plate-like sample immediately recovered its ring shape by dipping in hot water.
- ESO Polylactic acid
- Loloform (2 parts by mass of the total mass of ESO and polylactic acid) is mixed well at room temperature in various proportions as shown in Table 5 below.
- Acid catalyst (Sun-Aid SI-100 L) 1 mass (10 / ZL for 1.0 g ESO) was added and mixed well.
- This mixed solution was applied onto a glass plate using an applicator to form a film. After evaporating the black mouth form to some extent, the produced film was peeled off from the glass plate and cut into a size of 85 mm ⁇ 5 mm (sample thickness: 0.1 mm). This film was wrapped around a cylindrical glass tube and heated at 150 ° C. for 2 hours to obtain four annular samples (molded shapes) each.
- each of the obtained ring-shaped samples was heated, and the ring was opened to form a flat plate and held at 100 ° C. for 15 minutes, and then rapidly cooled in water to obtain a flat sample (deformed shape). The distance between both ends of this flat sample was measured. Next, this flat sample was heated on a hot plate at 100 ° C for 3 minutes, and the distance between both ends of this recovered shape was measured. Table 5 shows the average of the measurement results for each of the four samples.
- phase transition temperature of the obtained flat plate sample is a glass transition temperature of 60 ° C for PCL
- this sample is warmed to 80 ° C, and a helical shape is applied to a glass rod having an outer peripheral length of about 20 mm.
- a helical shape is applied to a glass rod having an outer peripheral length of about 20 mm.
- this helical sample was immersed in hot water of 10 ° C., it returned to its original flat plate shape.
- phase transition temperature of the obtained sample is the glass transition temperature of PVC 80 ° C
- the ring is opened and flattened, and then rapidly cooled to room temperature. It became flat (deformed). Then, when this flat sample was immersed in hot water at 100 ° C, it returned to its original spiral shape.
- phase transition temperature of the obtained flat plate sample is a glass transition temperature of PVC of 80 ° C
- this flat plate sample is heated to 80 ° C and a glass rod having an outer peripheral length of about 2 Omm. Wrapped in a spiral shape about twice, and then rapidly cooled to room temperature to obtain a helical sample.
- this helical sample was immersed in hot water at 80 ° C, it returned to its original flat plate shape.
- PBS poly (butylene succinate)
- an acid catalyst Sun-Aid S I-100 L
- This mixed solution was poured into a 44 mm ⁇ 5 mm ⁇ lmm fluororesin mold and heat-treated at 150 ° C. for 2 hours to obtain a flat plate sample (molded shape) having a thickness of about 1 mm.
- DSC differential scanning calorimetry
- phase transition temperatures are 60 ° C for PCL and 120 ° C for PBS. Therefore, as shown in Fig. 5, first, a flat sample (molded shape) was heated to 140 ° C, which is higher than the melting point of PBS, and deformed into a left-handed spiral shape (deformed shape 1). Next, when it was cooled to 80 ° C, which is below the melting point of PBS and above the melting point of PCL, and only PBS was crystallized, its helical shape (deformed shape 1) was retained. Furthermore, when it was deformed into a right-handed spiral shape (deformed shape 2) at that temperature and cooled to room temperature as it was, PCL was crystallized, and the shape (deformed shape 2) was retained.
- the phase transition temperatures are: the melting point of PCL is 60 ° C and the glass transition temperature of PVC is 80 ° C. Therefore, first, as shown in Fig. 7, it was heated to 100 ° C, which is a glass transition temperature of PVC of 80 ° C or higher, and was placed on a glass rod having an outer peripheral length of 44 mm. ). Next, when cooled to 65 ° C, which is higher than the melting point of PCL and lower than the glass transition temperature of PVC, the shape was retained. Furthermore, when the ring was opened at that temperature and deformed into a flat plate (deformed shape 2) and cooled to room temperature, the shape (deformed shape 2) was retained. Next, as shown in Fig. 8, when a flat sample (deformed shape 2) is heated to 65 ° C, it recovers to a loose helical shape, and when heated to 100 ° C, it becomes a helical shape (molded shape). Recovered.
- a shape memory resin in which a monomeric network polymer is used as a matrix, and a thermoplastic polymer chain is fixed in the matrix at a molecular level.
- the shape memory function can be expressed by using the morphological change of the phase change polymer in the network as an output. Therefore, the material characteristics can be freely adjusted according to the application, and can be easily applied to a wide range of resin combinations.
- the present shape memory resin is manufactured by a very simple method in which a thermoplastic polymer is dissolved in a network polymer precursor (for example, an epoxy compound) and cured at a temperature higher than the phase transition temperature of the thermoplastic polymer. obtain. This leads to a reduction in manufacturing costs.
- natural oils and epoxy compounds that are attracting attention as renewable resources can be effectively used as network polymer precursors in the present invention.
Abstract
Description
Claims
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US12/298,540 US20090131557A1 (en) | 2006-05-02 | 2007-04-26 | Shape memory resin |
JP2008514488A JP5083696B2 (ja) | 2006-05-02 | 2007-04-26 | 形状記憶樹脂 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2010033453A1 (en) * | 2008-09-17 | 2010-03-25 | Cornerstone Research Group, Inc. | Extrudable shape memory polymer |
JP2016041812A (ja) * | 2010-03-26 | 2016-03-31 | ジーカ テクノロジー アクチェンゲゼルシャフト | 構造用接着剤に基づく形状記憶材料 |
JP2016056377A (ja) * | 2010-03-26 | 2016-04-21 | ジーカ テクノロジー アクチェンゲゼルシャフト | 構造用接着剤に基づく形状記憶材料 |
WO2021205984A1 (ja) * | 2020-04-06 | 2021-10-14 | 学校法人日本大学 | 形状記憶性樹脂組成物及び成形体 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
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GB201012595D0 (en) | 2010-07-27 | 2010-09-08 | Zephyros Inc | Oriented structural adhesives |
WO2012027573A2 (en) | 2010-08-25 | 2012-03-01 | University Of Massachusetts | Biodegradable shape memory polymer |
CN107383898B (zh) * | 2011-05-31 | 2020-03-03 | 普立万公司 | 通过热-机械作用具有形状记忆的热塑性弹性体复合物 |
US9120898B2 (en) | 2011-07-08 | 2015-09-01 | Baker Hughes Incorporated | Method of curing thermoplastic polymer for shape memory material |
US8939222B2 (en) * | 2011-09-12 | 2015-01-27 | Baker Hughes Incorporated | Shaped memory polyphenylene sulfide (PPS) for downhole packer applications |
US8829119B2 (en) | 2011-09-27 | 2014-09-09 | Baker Hughes Incorporated | Polyarylene compositions for downhole applications, methods of manufacture, and uses thereof |
US9144925B2 (en) | 2012-01-04 | 2015-09-29 | Baker Hughes Incorporated | Shape memory polyphenylene sulfide manufacturing, process, and composition |
US9707642B2 (en) | 2012-12-07 | 2017-07-18 | Baker Hughes Incorporated | Toughened solder for downhole applications, methods of manufacture thereof and articles comprising the same |
WO2015011686A1 (en) | 2013-07-26 | 2015-01-29 | Zephyros Inc | Improvements in or relating to thermosetting adhesive films |
US10327871B2 (en) * | 2016-08-26 | 2019-06-25 | King Abdulaziz University | Reinforced gingival retraction cord |
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- 2007-04-26 JP JP2008514488A patent/JP5083696B2/ja not_active Expired - Fee Related
- 2007-04-26 WO PCT/JP2007/059442 patent/WO2007129681A1/ja active Search and Examination
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JPS6369864A (ja) * | 1986-09-12 | 1988-03-29 | Mitsubishi Rayon Co Ltd | 形状記憶性樹脂及びその使用方法 |
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WO2010033453A1 (en) * | 2008-09-17 | 2010-03-25 | Cornerstone Research Group, Inc. | Extrudable shape memory polymer |
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JP2016041812A (ja) * | 2010-03-26 | 2016-03-31 | ジーカ テクノロジー アクチェンゲゼルシャフト | 構造用接着剤に基づく形状記憶材料 |
JP2016056377A (ja) * | 2010-03-26 | 2016-04-21 | ジーカ テクノロジー アクチェンゲゼルシャフト | 構造用接着剤に基づく形状記憶材料 |
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WO2021205984A1 (ja) * | 2020-04-06 | 2021-10-14 | 学校法人日本大学 | 形状記憶性樹脂組成物及び成形体 |
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US20090131557A1 (en) | 2009-05-21 |
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