WO2019177110A1 - 極性オレフィン系重合体からなる成形品とその物性 - Google Patents

極性オレフィン系重合体からなる成形品とその物性 Download PDF

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WO2019177110A1
WO2019177110A1 PCT/JP2019/010592 JP2019010592W WO2019177110A1 WO 2019177110 A1 WO2019177110 A1 WO 2019177110A1 JP 2019010592 W JP2019010592 W JP 2019010592W WO 2019177110 A1 WO2019177110 A1 WO 2019177110A1
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Prior art keywords
olefin
polymer
copolymer
molded article
group
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English (en)
French (fr)
Japanese (ja)
Inventor
号兵 王
漾 ▲楊▼
正芳 西浦
侯　召民
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RIKEN
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RIKEN
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Priority to JP2020506652A priority Critical patent/JP7327815B2/ja
Priority to CN201980019050.5A priority patent/CN111868111B/zh
Priority to EP19766728.0A priority patent/EP3766906A4/en
Priority to US16/979,984 priority patent/US11535688B2/en
Publication of WO2019177110A1 publication Critical patent/WO2019177110A1/ja
Anticipated expiration legal-status Critical
Priority to US17/989,280 priority patent/US12291585B2/en
Priority to JP2023122151A priority patent/JP2023153162A/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F12/00—Homopolymers and 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 an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/16—Halogens
    • C08F212/18—Chlorine
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/16—Halogens
    • C08F212/20—Fluorine
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09D123/0892—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms containing monomers with other atoms than carbon, hydrogen or oxygen atoms
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/26—Nitrogen
    • C08F212/28—Amines
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/30—Sulfur
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/27—Amount of comonomer in wt% or mol%
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use 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 an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen

Definitions

  • the present invention relates to an olefin-based molded article containing a polar olefin-based polymer. More specifically, the present invention relates to an olefin-based molded article containing a polar olefin-based polymer having properties such as self-healing properties useful for various applications.
  • olefin-based molded products such as polyolefin films have been used in various ways as packaging materials, etc., but their use as high-functional molded products with special functions (for example, self-repairing and shape memory properties) Limited to departmental use.
  • high-performance self-healing materials not only will waste be reduced and sustainability will be achieved, but it will also be possible to create safer and more reliable products (non-patent literature) 1).
  • Self-healing materials are particularly attractive in applications where damage is difficult to detect and in applications where repair is expensive or impossible (such as medical implants in the human body, submarine pipelines, devices in space). Wool has built a unified theory based on De Gennes' reptation dynamics and an intertwined percolation model.
  • Non-patent Document 2 Several clear dynamic supramolecular approaches (metal-ligand interactions, polyvalent hydrogen bonds, etc.) have been established in pursuit of materials with intrinsic self-repairing properties (Non-patent Document 2). For now, however, improvements are limited to soft elastomers, and previous improvements include elaborately designed complex macromolecular structures. Most recently, Aida et al. Reported an amorphous polymer containing a series of hydrogen bonds that showed easy repairability and robust mechanical properties under specific pressure (Non-Patent Document 3). Thus, it has been a difficult task to develop a material having both an autonomous self-repairing action and strong mechanical properties.
  • the present invention has been made under such circumstances, and an object thereof is to provide a novel olefin-based molded article useful for various applications.
  • the present inventors have conducted intensive studies to solve the above problems.
  • the inventors of the present invention use a rare earth metal complex and a polar olefin polymer obtained by polymerizing a polar olefin monomer as a raw material for a molded article such as a film, and using the polymer. It has been found that molded articles such as films to be produced have various functions such as autonomous self-healing and shape memory. Based on such knowledge, the present invention has been completed.
  • the gist of the present invention is as follows.
  • An olefin-based molded article comprising a polymer containing a structural unit of at least one polar olefin monomer represented by the general formula (I).
  • CH 2 CH—R 2 —Z (R 1 ) n (I) Wherein Z is a heteroatom selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur and selenium, R 1 is a substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms, and n is Z And R 2 is a substituted or unsubstituted hydrocarbylene group having 2 to 20 carbon atoms.
  • the pre-copolymer is an alternating arrangement of the structural unit of the polar olefin monomer represented by the at least one general formula (I) and the structural unit of the at least one non-polar olefin monomer;
  • One embodiment of the olefin-based molded article according to [3] containing the copolymer exhibits an X-ray diffraction peak derived from a crystalline nanodomain formed by aggregation of the polymerization sequence.
  • Z is a heteroatom selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur and selenium
  • R 1 is a substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms
  • n is Z
  • R 3 is a hydrocarbylene group having 1 to 5 carbon atoms
  • R 4 is a halogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms.
  • Examples of the polymer used in the molded article of this embodiment include the (co) polymers described in the above [1] to [7]. Among these, the copolymer described in [7] is preferable.
  • the molded product preferably exhibits the toughness value in the above range at the use temperature of the molded product (for example, 25 ° C. when it is room temperature).
  • the molded product preferably has a tensile strength of 0.5 MPa or more and / or an elongation at break exceeding 100%.
  • the polymer used in the molded article of this embodiment include the (co) polymers described in the above [1] to [7]. Among these, the copolymer described in [7] is preferable.
  • the molded product preferably exhibits the tensile strength in the above range at the use temperature of the molded product (for example, 25 ° C. when it is room temperature).
  • the molded article preferably has a tensile strength in the above range, an elongation at break exceeding 100%, and / or a toughness value of 0.5 MJm ⁇ 3 or more.
  • the polymer used in the molded article of this embodiment include the (co) polymers described in the above [1] to [7]. Among these, the copolymer described in [7] is preferable. It is preferable that the molded article exhibits the elongation at break in the above range at the use temperature of the molded article (for example, 25 ° C.
  • the molded product preferably has an elongation at break in the above range, a toughness value of 0.5 MJm ⁇ 3 or more, and / or a tensile strength of 0.5 MPa or more.
  • Another embodiment of the present invention is a self-healing material comprising the olefin-based molded product of any one of [1] to [11] or including an olefin-based molded product.
  • Another aspect is a self-repairing molded article comprising the olefinic molded article of any one of the above [1] to [11] or including an olefinic molded article.
  • One embodiment of the self-repairing molded article contains the polymer exhibiting a glass transition point of less than room temperature (25 ° C.).
  • One embodiment of the self-healing molded article exhibits a self-healing rate of 80% or more within 5 days.
  • Another embodiment of the present invention is a shape memory material comprising the olefin-based molded product of any one of [1] to [11] or including an olefin-based molded product.
  • Another aspect is a shape memory molded article comprising the olefinic molded article of any one of [1] to [11] or including an olefinic molded article.
  • One embodiment of the shape memory molded product contains the polymer having a glass transition point of about room temperature (for example, 15 ° C. to 35 ° C.) or higher than room temperature.
  • the shape memory molded article maintains a constant shape S1 at a temperature (for example, room temperature) Tu at which it is used, and a temperature exceeding Tg (Tu ⁇ Tg) (and a temperature below the melting point if it has a melting point). ) It deforms at Td and maintains its shape S2 by cooling to the use temperature Tu, and a temperature exceeding Tg (and a temperature below the melting point if it has a melting point) Tf (Tf is the same as or different from Td) May have a property of returning to the original shape S1.
  • One aspect of the shape memory molded product has a shape fixing rate and a shape recovery rate of 80% or more.
  • a novel olefin-based molded article useful for various applications can be provided.
  • FIG. 1 is a diagram showing the structure of the metallocene complex used in the examples.
  • FIG. 2 is a diagram showing the structure of the polar olefin monomer used in the examples.
  • FIG. 3 is a diagram showing the analytical value and 1 H NMR spectrum of polymer P2 obtained in Run 3 of Table 1.
  • FIG. 4 is a diagram showing a 13 C NMR spectrum of polymer P2 obtained in Run 3 of Table 1.
  • FIG. 5 is a diagram showing a partial enlarged view of the analysis value and 13 C NMR spectrum of polymer P2 obtained in Run 3 of Table 1.
  • FIG. 6 is a diagram showing a DSC curve of the polymer P2 obtained by Run 3 in Table 1.
  • FIG. 1 is a diagram showing the structure of the metallocene complex used in the examples.
  • FIG. 2 is a diagram showing the structure of the polar olefin monomer used in the examples.
  • FIG. 3 is a diagram showing the analytical value and 1 H NMR spectrum of polymer P2 obtained in
  • FIG. 7 is a diagram showing a transmission spectrum of a film sample of 0.5 mm thickness of copolymer P2. Inside is a picture (photo) of the film placed on top of the logo.
  • FIG. 8 is a diagram showing the mechanical properties of the copolymers P1-P5. A is a stress-strain curve at a speed of 200 mm min ⁇ 1 . B is a tensile strength / hysteresis curve of the copolymer P5. Ten cycles of 1000% elongation were performed. Inside, after 10 cycles of 1000% elongation and recovery (top) and its original form (bottom) (photo).
  • FIG. 9 is a diagram showing the analysis value and 1 H NMR spectrum of polymer P6 obtained in Run 5 of Table 3.
  • FIG. 10 is a diagram showing a 13 C NMR spectrum of polymer P6 obtained in Run 5 of Table 3.
  • FIG. 11 is a diagram showing a partially enlarged view of the analysis value and 13 C NMR spectrum of polymer P6 obtained in Run 5 of Table 3.
  • FIG. 12 is a diagram showing a DSC curve of polymer P6 obtained in Run 5 in Table 3.
  • FIG. 13 is a diagram showing the analytical value and 1 H NMR spectrum of polymer P7 obtained in Run 7 of Table 3.
  • FIG. 14 is a diagram showing a 13 C NMR spectrum of polymer P7 obtained in Run 7 of Table 3.
  • FIG. 15 is a diagram showing a partial enlarged view of the analytical value and 13 C NMR spectrum of polymer P7 obtained in Run 7 of Table 3.
  • FIG. 16 is a diagram showing a DSC curve of polymer P7 obtained by Run 7 in Table 3.
  • FIG. 17 is a diagram showing an analytical value and a 1 H NMR spectrum of the polymer obtained in Run 9 of Table 3.
  • FIG. 18 is a diagram showing a 13 C NMR spectrum of the polymer obtained in Run 9 of Table 3.
  • FIG. 19 is a diagram showing a partial enlarged view of the analytical value and 13 C NMR spectrum of the polymer obtained in Run 9 of Table 3.
  • FIG. 20 is a diagram showing a DSC curve of the polymer obtained in Run 9 in Table 3.
  • FIG. 21 is a diagram showing the analytical value and 1 H NMR spectrum of polymer P8 obtained in Run 11 of Table 3.
  • FIG. 22 is a diagram showing a 13 C NMR spectrum of polymer P8 obtained in Run 11 of Table 3.
  • FIG. 23 is a diagram showing a partial enlarged view of the analysis value and 13 C NMR spectrum of polymer P8 obtained in Run 11 of Table 3.
  • FIG. 24 is a diagram showing a DSC curve of polymer P8 obtained with Run 11 in Table 3.
  • FIG. 25 is a diagram showing the analytical value and 1 H NMR spectrum of polymer P9 obtained in Run 13 of Table 3.
  • FIG. 26 is a diagram showing a 13 C NMR spectrum of polymer P9 obtained in Run 13 of Table 3.
  • FIG. 27 is a diagram showing a partial enlarged view of the analytical value and 13 C NMR spectrum of polymer P9 obtained in Run 13 of Table 3.
  • FIG. 28 is a diagram showing a DSC curve of the polymer P9 obtained by Run 13 in Table 3.
  • FIG. 29 is a diagram showing the analytical value and 1 H NMR spectrum of polymer P10 obtained in Run 15 of Table 3.
  • FIG. 30 is a diagram showing a 13 C NMR spectrum of the polymer P10 obtained in Run 15 of Table 3.
  • FIG. 31 is a diagram showing a partial enlarged view of the analytical value and 13 C NMR spectrum of polymer P10 obtained in Run 15 of Table 3.
  • FIG. 32 is a diagram showing a DSC curve of polymer P10 obtained with Run 15 in Table 3.
  • FIG. 33 is a diagram showing the mechanical properties of the copolymer P6-P10.
  • A is a stress-strain curve of the copolymer P6-P10 at a speed of 200 mm min ⁇ 1 .
  • B is the tensile strength / hysteresis curve of copolymer P6. Ten cycles of 1000% elongation were performed.
  • C is a tensile strength / hysteresis curve of the copolymer P7.
  • FIG. 34 is a diagram showing the self-healing property of an alternating AP-E copolymer film.
  • A is an optical image (photograph) of a ruptured state (bottom) of a film sample of copolymer P2 and a stretched state (top) after recovery at 25 ° C. for 5 minutes. Break samples were prepared by completely cutting the film into two separate parts using a razor blade. The repaired samples were brought together in the air at 25 ° C. for 5 minutes after the cut surfaces were matched and lightly pressed for 15 seconds.
  • B is a stress-strain curve showing the test result of the self-healing property of copolymer P2 at 25 ° C. in air.
  • C is a stress-strain curve showing the test result of the self-healing property of copolymer P5 at 25 ° C. in air.
  • D is an optical microscopic image (photograph) of a damaged (left) and repaired (right) sample of copolymer P5 at 25 ° C. in air. The copolymer P5 film was cracked with a razor blade and allowed to recover in air for 5 minutes.
  • E is an optical microscopic image (photograph) of a damaged (left) and repaired (right) sample of copolymer P2 at 25 ° C. in water.
  • F is a stress-strain curve showing the test result of the self-healing property of copolymer P2 at 25 ° C. in water.
  • G is a stress-strain curve showing the self-healing test result of the copolymer P2 at 37 ° C. in water.
  • H is a stress-strain curve showing the results of a comparative test of the self-healing property of (iii) 1M HCl and (iv) 1M NaOH in 25 ° C (ii) water for 36 hours of the copolymer P2.
  • I is a stress-strain curve showing the test result of the self-healing property of copolymer P6 at 25 ° C. in air.
  • J is a stress-strain curve showing the test result of the self-healing property of copolymer P7 at 25 ° C. in air.
  • K is a stress-strain curve showing the test result of the self-healing property of copolymer P8 at 25 ° C. in air.
  • L is a stress-strain curve showing the test results of the self-healing property of the copolymer of Run 9 in Table 3 at 25 ° C. in air.
  • FIG. 35 is a diagram (photograph) showing the shape memory property of the copolymer P10.
  • FIG. 36 is a view showing a state of a predetermined polymer contained in an example of the molded article of the present invention.
  • A shows a TEM image (photo).
  • B is a schematic diagram.
  • the curve represents an alternating chain of a polar olefin monomer (A) such as anisylpropylene and a nonpolar olefin monomer (B) such as ethylene-(A) -alt- ( B)-, and a circle indicates a crystalline nanodomain generated by aggregation of a homopolymerized sequence-(B)-(B)-of a nonpolar olefin monomer (B) such as ethylene.
  • FIG. 37 shows the WAXD measurement results of the polymer P5 film produced in the example.
  • FIG. 38 shows SAXS measurement results of the polymer P5 film produced in the example.
  • FIG. 39 is a diagram (photograph) showing the shape memory property of a film sample of copolymer P9 produced in Example.
  • a is an original form of a molded sample of the copolymer P9.
  • b is a deformation of a sample of molded copolymer P9 stretched at 50 ° C.
  • c shows a state in which the sample of b maintains a deformed shape at 20 ° C.
  • d is a sample of the molded copolymer P9 recovered to its original shape in 5 seconds in a 50 ° C. water bath.
  • FIG. 40 is a graph showing a dual shape memory cycle at 50 ° C. of a film sample of copolymer P9 produced in the example.
  • olefinic system obtained by one-step polymerization using a scandium complex of a polar olefin monomer represented by a predetermined formula (for example, anisylpropylene (derivative)).
  • a predetermined formula for example, anisylpropylene (derivative)
  • This new material is useful as a raw material for a molded product (for example, a film).
  • the copolymer with a non-polar olefin monomer has an alternating non-polar monomer (eg ethylene) -polar olefin monomer (eg anisylpropylene (derivative)) sequence, the polymerization ratio of each monomer, By adjusting one or more of molecular weight, monomer type, etc., it has a wide glass transition temperature range and exhibits various mechanical properties (hard plastic, soft plastic, elastomer and stress softening material).
  • One embodiment of the material is an elastomer and is a self-healing material.
  • the elastomer showed excellent stretchability and elastic recovery, and the self-repairing elastomer showed high tensile strength and toughness.
  • Autonomous self-healing elastomers are capable of self-healing not only in air, but also in water, acid, alkaline solutions, without the need for external energy or stimulation. Even more surprising, the repaired material exhibits excellent tensile strength and elongation, and is higher than the self-healing material after self-healing and the self-healing material before self-healing reported so far.
  • Another embodiment of the material is a hard plastic and exhibits remarkable shape memory.
  • the present invention relates to an olefin-based molded article containing a polymer containing a structural unit of at least one polar olefin monomer represented by the general formula (I).
  • CH 2 CH—R 2 —Z (R 1 ) n (I)
  • Z is a heteroatom selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur and selenium
  • R 1 is a substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms
  • n is Z
  • R 2 is a substituted or unsubstituted hydrocarbylene group having 2 to 20 carbon atoms.
  • a polymer containing a structural unit of at least one polar olefin monomer represented by the general formula (I) contained in the olefin-based molded article of the present invention that is, at least one polymer represented by the general formula (I).
  • a method for producing a polymer of a polar olefin monomer (hereinafter also referred to as “polar olefin polymer”) will be described.
  • the term “polymer” is used to mean including a homopolymer and a copolymer unless otherwise specified.
  • the polar olefin polymer is obtained, for example, by polymerizing at least one polar olefin monomer represented by the general formula (I) with a catalyst composition containing a metallocene complex and an ionic compound. You may make it copolymerize with other monomers other than the polar olefin monomer represented by general formula (I), and the polar olefin polymer copolymerized with at least 1 sort (s) of the nonpolar olefin monomer is especially preferable.
  • the metallocene complex but not limited to, for example, a scandium complex (C 5 Me 4 SiMe 3) Sc (CH 2 C 6 H 4 NMe 2 -o) 2 or the like described in the Examples.
  • Metallocene complexes can be prepared by the methods described above, for example, (1) X. Li, M. Nishiura, K. Mori, T. Mashiko, Z. Hou, Chem. Commun. 4137-4139 (2007), (2) M. Nishiura , J. Baldamus, T. Shima, K. Mori, Z. Hou, Chem. Eur. J. 17, 5033-5044 (2011)., (3) F. Guo, M. Nishiura, H. Koshino, Z. Hou, Macromolecules. 44, 6335-6344 (2011)., (4) References: Tardif, O .; Nishiura, M .; Hou, Z. M.
  • the ionic compound is combined with the metallocene complex described above to cause the metallocene complex to exhibit activity as a polymerization catalyst. As the mechanism, it can be considered that the ionic compound reacts with the metallocene complex to generate a cationic complex (active species).
  • the ionic compound contained in the said catalyst composition is not limited, What combined each chosen from a non-coordinating anion and a cation is mentioned.
  • triphenylcarbonium tetrakis (pentafluorophenyl) borate triphenylcarbonium tetrakis (tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocete Examples thereof include nium tetrakis (pentafluorophenyl) borate.
  • One ionic compound may be used, or two or more ionic compounds may be used in combination.
  • triphenylcarbonium tetrakis (pentafluorophenyl) borate are particularly preferred.
  • the molar ratio of the ionic compound to the metallocene complex varies depending on the type of the complex and the ionic compound, and can be set as appropriate.
  • the ionic compound is composed of a carbonium cation and a boron anion (for example, [Ph 3 C] [B (C 6 F 5 ) 4 ])
  • the molar ratio is based on the central metal of the metallocene complex.
  • the alkylaluminum compound such as methylaluminoxane is preferably about 10 to 4000 with respect to the central metal of the metallocene complex.
  • the ionic compound is considered to be a catalytically active species by ionizing, i.e., cationizing, the metallocene complex, and can sufficiently activate the metallocene complex within the above-described ratio range, and carbonium.
  • An ionic compound composed of a cation and a boron anion does not become excessive, and the possibility of causing an undesired reaction with a monomer to be polymerized can be reduced.
  • a polar olefin monomer is polymerized (addition polymerization), preferably a nonpolar olefin monomer and a polar olefin monomer are polymerized (addition polymerization) to produce an olefin polymer.
  • a composition containing each component such as a metallocene complex and an ionic compound
  • providing each component separately in the polymerization reaction system By constituting the composition, it can be used as a polymerization catalyst composition.
  • “providing as a composition” includes providing a metallocene complex (active species) activated by reaction with an ionic compound.
  • the production method of the polymer can be performed, for example, by the following procedure.
  • a polymerizable monomer is supplied and polymerized in a system (preferably a liquid phase) containing a catalyst composition used in the polymer production method.
  • the monomer if it is liquid, it can be supplied by dropping, and if it is gas, it can be supplied through a gas pipe (for example, bubbling if it is a liquid phase reaction system).
  • Polymerization is carried out by adding the catalyst composition used in the method for producing the polymer to the system containing the polymerizable monomer (preferably the liquid phase) or by separately adding the components of the catalyst composition.
  • the catalyst composition to be added may be prepared in advance (preferably prepared in a liquid phase) and activated (in this case, it is preferable to add the catalyst composition so as not to touch outside air).
  • the production method may be any method such as a gas phase polymerization method, a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a solid phase polymerization method.
  • the solvent used is not particularly limited as long as it is inactive in the polymerization reaction and can dissolve the monomer and the catalyst and does not interact with the catalyst.
  • saturated aliphatic hydrocarbons such as butane, pentane, hexane and heptane; saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene and toluene; methylene chloride, chlorobenzene, bromobenzene and chloro And halogenated hydrocarbons such as toluene.
  • the solvent which does not have toxicity with respect to a biological body is preferable.
  • an aromatic hydrocarbon, particularly toluene is preferable.
  • the solvent may be used alone or in combination of two or more.
  • the amount of the solvent to be used is arbitrary, but for example, it is preferable that the concentration of the complex contained in the polymerization catalyst is 1.0 ⁇ 10 ⁇ 5 to 1.0 ⁇ 10 ⁇ 1 mol / L. .
  • the amount of the monomer to be subjected to the polymerization reaction can be appropriately set according to the intended polymer to be produced.
  • the monomer is 100 times or more and 200 times in molar ratio to the metallocene complex constituting the polymerization catalyst composition. As mentioned above, it is preferable to make it 500 times or more.
  • the polymerization temperature may be any temperature, for example, in the range of ⁇ 90 to 100 ° C. Although it may be appropriately selected according to the type of monomer to be polymerized, etc., it can usually be performed at around room temperature, that is, at about 25 ° C.
  • the polymerization time is about several seconds to several days, and may be appropriately selected according to the type of monomer to be polymerized. It may be 1 hour or less, and in some cases 1 minute or less.
  • these reaction conditions can be appropriately selected according to the polymerization reaction temperature, the type and molar amount of the monomer, the type and amount of the catalyst composition, etc., and should be limited to the ranges exemplified above. There is no.
  • the said polymer as a copolymer
  • the polar olefin monomer used in the method for producing the polymer is a polar olefin monomer containing a polar group.
  • it is a polar olefin monomer represented by the following general formula (I).
  • CH 2 CH—R 2 —Z (R 1 ) n
  • Z in the general formula (I) is a heteroatom selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur and selenium
  • R 1 is a substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms
  • the heteroatom in the polar olefin monomer interacts with the central metal of the catalyst to form an intramolecular chelate, thereby promoting the interaction between the catalyst and the olefin unit. It is considered that the polymerization activity is promoted and the original stereoselectivity is exhibited.
  • R 1 in the general formula (I) is not limited as long as an intramolecular interaction in a polymerization reaction between the hetero atom in the polar group of the polar olefin monomer, the olefin unit, and the central metal of the catalyst is formed.
  • R 1 is a substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, 1 to 10 carbon atoms, linear or branched chain having 1 to 6 carbon atoms,
  • the number of alkyl groups, alkenyl groups, or alkynyl groups that are substituents and the substitution position in the cyclic alkyl group are not particularly limited); aryl groups; alkyl groups, alkenyl groups, or alkynyl groups having 1 to 10 carbon atoms (The number of alkyl groups, alkenyl groups, or alkynyl groups that are substituent groups and the substitution position in the aryl group are
  • the hydrocarbyl group in the substituted hydrocarbyl group is the same as the hydrocarbyl group described above.
  • the substituted hydrocarbyl group is a hydrocarbyl group in which at least one hydrogen atom of the hydrocarbyl group is substituted with a halogen atom or the like.
  • R 2 functions as a spacer for connecting the polar group and the olefin part in the polar olefin monomer.
  • R 2 is not limited as long as an intramolecular interaction in a polymerization reaction between the hetero atom in the polar group of the polar olefin monomer, the olefin unit, and the central metal of the catalyst is formed.
  • R 2 preferably has 2 to 20 carbon atoms.
  • the carbon number of R 2 depends on the type of heteroatom represented by Z, the type of substituent represented by R 1 , etc., using polymerization activity as an index, A carbon number suitable for forming an intramolecular interaction in the polymerization reaction can be selected.
  • R 2 is a hydrocarbylene group having 2 to 11 carbon atoms. More preferably, they are a linear or branched alkylene group having 2 to 3 carbon atoms; a cyclic alkylene group having 3 to 11 carbon atoms; an arylene group having 6 to 11 carbon atoms; or an aralkylene group having 7 to 11 carbon atoms.
  • substituent for R 2 include a halogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. Can be mentioned.
  • One form of the compound represented by the general formula (I) is a compound represented by the general formula (II).
  • Z, R 1 and n in the general formula (II) have the same definitions as those described in the general formula (I).
  • Z in the general formula (II) is preferably oxygen.
  • R 1 in the general formula (II) is preferably a linear, branched or cyclic alkyl group having 1 to 3 carbon atoms.
  • the bonding position of —Z (R 1 ) n in the aromatic ring is not limited, but is preferably the o position.
  • R 3 is a hydrocarbylene group having 1 to 5 carbon atoms. More preferably, they are a linear or branched alkylene group having 1 to 3 carbon atoms; a cyclic alkylene group having 3 to 5 carbon atoms.
  • R 4 as a substituent of the aromatic ring is a halogen atom, a hydrocarbyl group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. And when R 4 is a hydrocarbyl group, they may combine to form a saturated, unsaturated or hetero-fused ring.
  • the substitution position of R 4 in the aromatic ring is not limited, but is preferably the m position. m is an integer of 0-4. More preferably, m is 0-2.
  • the hydrocarbyl group having 1 to 10 carbon atoms is more preferably a linear, branched alkyl group, alkenyl group, or alkynyl group having 1 to 6 carbon atoms, and more preferably a methyl group, an ethyl group, Examples include n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and the like.
  • the alkylthio group having 1 to 10 carbon atoms is an alkylthio group having 1 to 6 carbon atoms, such as methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec -Butylthio group, tert-butylthio group, n-pentylthio group, n-hexylthio group and the like.
  • the alkylamino group having 1 to 10 carbon atoms is more preferably an alkylamino group having 1 to 6 carbon atoms.
  • the alkylamino group may be a dialkylamino group, and the alkyl substituting the amino group may be the same or different alkyl. More preferably, the alkylamino group is a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a diisobutylamino group, a disec-butylamino group, or a ditert-butylamino group. And dialkylamino groups such as groups.
  • the alkoxy group having 1 to 10 carbon atoms is more preferably an alkoxy group having 1 to 3 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group.
  • R 4 is bonded to each other, the saturated condensed ring R 4 is an aromatic ring condensed with formation of substituted, a naphthalene ring, etc..
  • the hetero-fused ring formed by condensing R 4 with each other and the aromatic ring substituted by R 4 includes indole ring, isoindole ring, quinoline ring, isoquinoline ring, carbazole ring, acridine ring, benzofuran ring, benzopyran ring And benzothiophene ring.
  • the condensed ring may have 1 to 6 substituents, and the substituents are the same as those for R 4 above.
  • the compound represented by the general formula (II) include 2-allyl-4-fluoroanisole, 2-allyl-4,5-difluoroanisole, 2-allyl-4-methylanisole, 2-allyl-4 Substituted 2-allyl anisole such as 2-tert-butylanisole, 2-allyl-4-hexylanisole, 2-allyl-4-methoxyanisole, 3- (2-methoxy-1-naphthyl) -1-propylene (hereinafter, also referred to as "AP R”); unsubstituted 2-allyl anisole (3- (2-anisyl) -1-propylene) (hereinafter, also referred to as "AP”); but the like, but not limited to.
  • 2-allyl-4-fluoroanisole such as 2-tert-butylanisole, 2-allyl-4-hexylanisole, 2-allyl-4-methoxyanisole, 3- (2-methoxy-1-naphthyl) -1-propylene (herein
  • the polar monomer used in the polymerization reaction may be used alone or in combination of two or more.
  • Non-polar olefin monomer The polar monomer may be copolymerized with another monomer (preferably a nonpolar olefin monomer).
  • the nonpolar olefin monomer is not particularly limited as long as it is addition-polymerizable and can be copolymerized with the polar olefin monomer.
  • Cyclic olefins including norbornenes such as 2-norbornene and dicyclopentadiene, and cyclohexadiene).
  • ⁇ -olefin examples include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.
  • a straight chain ⁇ -olefin having 3 to 20 carbon atoms such as 4-methyl-1-pentene, 3-methyl-1-pentene, 3-methyl-1-butene and the like having 4 to 20 carbon atoms. Examples thereof include chain ⁇ -olefins.
  • dienes that are olefinic monomers include 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,4 -Linear dienes having 3 to 20 carbon atoms such as hexadiene, such as 2-methyl-1,3-butadiene, 2,4-dimethyl-1,3-pentadiene, 2-methyl-1,3-hexadiene Examples thereof include branched diene having 4 to 20 carbon atoms and cyclic diene having 4 to 20 carbon atoms such as cyclohexadiene.
  • the nonpolar olefin monomer used in the copolymerization reaction may be used alone or in combination of two or more.
  • polar olefin monomer and the non-polar olefin monomer those synthesized based on a conventional method in the field of organic chemistry can be used. Moreover, you may use what is marketed.
  • the olefin-based molded article of the present invention includes a polar olefin-based polymer that is a polymer including a structural unit of a polar olefin monomer represented by at least one general formula (I).
  • the ratio of the polar olefin structural unit is preferably 20 mol% or more, more preferably 30 mol% or more, 40 mol% or more, in terms of molar ratio. 50 mol% or more, 60 mol% or more, 70 mol% or more, or 80 mol% or more is contained.
  • the molecular weight distribution of a polymer is arbitrary, the polymer with a comparatively narrow molecular weight distribution can also be used preferably.
  • the molecular weight distribution may be a value (Mw / Mn) measured by a GPC method (measured at 145 ° C. using polystyrene as a standard substance and 1,2-dichlorobenzene as an eluent). It can be measured using (TOSOH HLC 8321 GPC / HT).
  • the molecular weight distribution of the polymer is usually such that its index Mw / Mn is 5.0 or less, preferably 4.0 or less and 3.0 or less.
  • the number average molecular weight of the polymer is arbitrary, but a polymer having a relatively high number average molecular weight can also be preferably used.
  • the number average molecular weight (g / mol) varies depending on the structure of the structural unit derived from the polar olefin monomer, the ratio of the structural unit derived from the polar olefin monomer, and the like.
  • the viewpoint of achieving characteristics such as shape memory property it is usually 2.0 ⁇ 10 3 or more, preferably 3.0 ⁇ 10 3 or more, 10 ⁇ 10 3 or more, 50 ⁇ 10 3 or more, 80 ⁇ 10 3 or more, 100 ⁇ 10 3 or more, 150 ⁇ 10 3 or more, 200 ⁇ 10 3 or more, 250 ⁇ 10 3 or more, 300 ⁇ 10 3 or more, 350 ⁇ 10 3 or more, 400 ⁇ 10 3 or more, 450 ⁇ 10 3 or more, 500 ⁇ 10 3 or more and 1000 ⁇ 10 3 or more.
  • the glass transition point (Tg) of the polymer can vary depending on the structure of the structural unit derived from the polar olefin monomer.
  • the glass transition point is not particularly limited, but is usually about ⁇ 40 to 100 ° C.
  • the glass transition point can be measured by a differential scanning calorimetry (DSC) method or the like.
  • DSC differential scanning calorimetry
  • the Tg of the polymer used as a raw material is below room temperature (generally 25 ° C., but may vary depending on the mode and conditions used). Is preferred.
  • the Tg of the polymer used as a raw material exceeds room temperature (generally 25 ° C., but may vary depending on the mode and conditions used). It is preferable.
  • the polymer When the polymer has a melting point, it varies depending on the structure of the structural unit derived from the polar olefin monomer, the ratio of the structural unit derived from the polar olefin monomer, etc., but is usually 100 ° C. or higher, preferably 110 ° C. or higher, preferably 120 ° C. or higher, It is 130 ° C or higher.
  • the melting point can be measured, for example, by a differential scanning calorimetry (DSC) method.
  • a copolymer of the polar olefin monomer and ethylene (nonpolar olefin monomer) will be described as an example.
  • the copolymer is a copolymer having a structural unit derived from a polar olefin monomer represented by the following formula (A) and a structural unit derived from ethylene represented by the formula (B).
  • R 1, R 2, n is the same as Z, R 1, R 2, n described above in the general formula (I).
  • the structural units represented by the above formulas (A) and (B) may be arranged in any order. That is, both may be arranged at random, or arranged with some regularity (for example, the structural units of (A) and (B) are arranged alternately, and each is arranged to some extent continuously. May be arranged in any other order).
  • the copolymer may be a random copolymer, an alternating copolymer, a block copolymer, or other ordered copolymer.
  • the copolymer is preferably an alternating copolymer.
  • the alternating copolymer is an array in which structural units (A) and (B) are alternately arranged as a main array (hereinafter referred to as “alternate (A)-(B) array” or “(A) -alt”).
  • -(B) also referred to as an "array”
  • the sub-arrays may include an array in which each of the sub-arrays is continuously arranged to some extent.
  • the copolymer is an alternating copolymer, and the ratio of alternating (A)-(B) sequences in the entire sequence of the copolymer (two or more polar olefin monomer structural units and two or more nonpolar olefins)
  • the molar ratio of the total number of alternating arrangements of the polar olefin monomer structural unit and the nonpolar olefin monomer structural unit is usually 30 mol% or more, preferably 40 mol% or more, 50 mol%. As mentioned above, 60 mol% or more and 70 mol% or more are included.
  • each of the polymer sequences (A) and (B) may be included together with the alternating sequence-(A) -alt- (B)-. Containing (A) -alt- (B)-and the polymerization sequence of (B)-(B)-(B)-contributes to the functional expression of the molded article of the present invention, as will be described later. I think so.
  • the sequence ratio can be measured, for example, by 1 H-NMR, 13 C-NMR, or the like. Specifically, it can be determined by comparing the integral ratio of the peak of 1.0 to 1.5 ppm by 1 H-NMR.
  • the contents of the structural unit of the formula (A) and the structural unit of the formula (B) contained in the copolymer are arbitrary.
  • the proportion of the structural unit of the formula (A) can be 1 to 99 mol% in terms of molar ratio.
  • it can also be set as the copolymer in which the ratio of the polar olefin structural unit in a copolymer is comparatively high.
  • the copolymer contained in the olefin-based molded article has a sufficiently high ratio of structural units of the formula (A), so that the alternating (A)- (B) It can have the ratio of arrangement
  • the mechanical characteristics such as high toughness have a sufficiently high balance between a sufficiently high tensile strength and a sufficiently high elongation at break.
  • the proportion of the polar olefin structural unit in the copolymer is the molar ratio of the structural unit of the formula (A). The ratio is usually 20 mol% or more, preferably 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, 70 mol% or more, or 80 mol% or more.
  • the proportion of the structural unit can be measured by, for example, 1 H-NMR, 13 C-NMR, or the like. Specifically, it can be determined by comparing the integral ratio of methylene or methyl hydrogen adjacent to the hetero atom and the hydrocarbon at 1-1.8 ppm by 1 H-NMR.
  • the proportion of the structural unit is controlled by adjusting the ratio of each monomer as a raw material in the production of the copolymer.
  • the content rate of the structural unit of a formula (A) becomes high, the adhesiveness with a polar material, compatibility, etc. which are the characteristics by the polar group of a polar olefin monomer can be exhibited effectively.
  • the copolymer can have a high molecular weight, the entanglement point is increased, and it is advantageous in that an improvement in compatibility and adhesiveness can be expected.
  • the molecular weight distribution of the copolymer is arbitrary, but a copolymer having a relatively narrow molecular weight distribution can also be preferably used.
  • the molecular weight distribution may be a value (Mw / Mn) measured by a GPC method (measured at 145 ° C. using polystyrene as a standard substance and 1,2-dichlorobenzene as an eluent). It can be measured using (TOSOH HLC 8121 GPC / HT).
  • the molecular weight distribution of the copolymer is usually such that its index Mw / Mn is 5.0 or less, preferably 4.0 or less and 3.0 or less.
  • the number average molecular weight of the copolymer is arbitrary, but a copolymer having a relatively high number average molecular weight can also be preferably used.
  • the number average molecular weight (g / mol) varies depending on the structure of the structural unit derived from the (non) polar olefin monomer, the ratio of the structural unit derived from the polar olefin monomer and the structural unit derived from the nonpolar olefin monomer, and the like.
  • the viewpoint of achieving characteristics such as high mechanical properties, autonomous self-repairing action, and shape memory property it is usually 2.0 ⁇ 10 3 or more, preferably 3.0 ⁇ 10 3 or more, preferably 10 ⁇ 10 3 or more, 50 ⁇ 10 3 or more, 80 ⁇ 10 3 or more, 100 ⁇ 10 3 or more, 150 ⁇ 10 3 or more, 200 ⁇ 10 3 or more, 250 ⁇ 10 3 or more, 300 ⁇ 10 3 or more, 350 ⁇ 10 3 or more, 400 ⁇ 10 3 or more, 450 ⁇ 10 3 or more, 500 ⁇ 10 3 or more, 1000 ⁇ 10 3 or more.
  • the glass transition point (Tg) of the copolymer can vary depending on the structure of the structural unit derived from the polar olefin monomer.
  • the glass transition point is not particularly limited, but is usually about ⁇ 40 to 100 ° C.
  • the glass transition point can be measured by a differential scanning calorimetry (DSC) method or the like.
  • the Tg of the copolymer used as a raw material is the use temperature (for example, when the room temperature is the use temperature, it is generally 25 ° C, (It may vary depending on the conditions) Further, in order to obtain a shape memory molded product, the Tg of the copolymer used as a raw material is used at a use temperature (for example, generally 25 ° C. when room temperature is a use temperature). It may preferably vary depending on the mode and conditions.
  • the copolymer has a melting point, it varies depending on the structure of the structural unit derived from the (non-) polar olefin monomer, the ratio of the structural unit derived from the polar olefin monomer to the structural unit derived from the non-polar olefin monomer, and the like. ° C or higher, preferably 110 ° C or higher, 120 ° C or higher, or 130 ° C or higher.
  • the melting point can be measured, for example, by a differential scanning calorimetry (DSC) method.
  • One aspect of the copolymer according to the present invention includes structural units represented by the following formulas (III) and (IV), respectively.
  • x and y show the ratio (molar ratio) of each structural unit in the whole arrangement
  • R 1 , R 3 , R 4 , Z, m and n have the same meanings as those in the formula (II), and preferred ranges are also the same.
  • x and y represent the proportion of each structural unit, and are positive numbers satisfying x> 0, y> 0, x> y, and 80% ⁇ x + y ⁇ 100%.
  • x + y is preferably 85% or more, 90% or more, 95% or more, or 97% or more.
  • the olefin-based molded article of the present invention is an olefin-based molded article containing at least one polymer of a polar olefin monomer represented by the general formula (I).
  • One embodiment of the olefin-based molded article of the present invention has an alternating ethylene- (substituted) anisylpropylene sequence, and has an autonomous self-healing action and excellent mechanical properties.
  • the mechanism with autonomous self-healing action and excellent mechanical properties is that the polar olefin copolymer has an alternating ethylene- (substituted) anisylpropylene sequence as a side chain in the backbone of the alternating ethylene-propylene copolymer It is considered that (substituted) anisyl groups are regularly distributed. This may have enhanced molecular entanglement between damaged surfaces and between polymer chains without being severely affected by water, acid, or base.
  • self-healing that is, autonomous self
  • self-healing without the need for external energy or stimulation (pressure, temperature, etc.) not only in air but also in water, acid, or alkaline solution.
  • External energy or stimulation pressure, temperature, etc.
  • pressure, temperature, etc. is not particularly necessary for the self-repairing action of the olefin-based molded article of the present invention, but these can be added.
  • external energy or stimulus pressure, temperature, etc.
  • self-healing means that the entanglement of the copolymer chain occurs again by bringing damage such as scratches or cut surfaces of the molded product into contact with each other, and returns to the shape, physical properties, etc. of the molded product before the damage.
  • the self-repairing action can be confirmed, for example, by bringing damage into contact, leaving it in a predetermined environment at a predetermined temperature for a predetermined time, and comparing the shape, physical properties, etc. after the damage with those before the damage. Specifically, it can be confirmed by, for example, the method described in Examples below.
  • the self-healing efficiency of the olefin-based molded article of the present invention varies depending on the type of copolymer used and the like, and is not limited.
  • the elongation at break after damage is usually 50% or more, preferably 60% or more, 70% or more of the elongation before damage. % Or more, 80% or more, 90% or more, 95% or more, 99% or more, 100%.
  • One aspect of the self-repairing molded article is a copolymer having structural units represented by the above formulas (III) and (IV), respectively, and the Tg is the use temperature (for example, the use temperature is room temperature) Is a molded article containing the copolymer which is generally 25 ° C. or less.
  • a self-healing rate of 80% or more can be achieved.
  • the time for achieving the self-healing rate is not particularly limited, and includes the type of polymer used (more specifically, a copolymer having a structural unit represented by each of the above formulas (III) and (IV)).
  • a self-healing rate of 80% or more can be achieved in 5 days.
  • one form of the olefin type molded product of the present invention is an olefin type molded product having a shape memory action.
  • shape memory action means that a primary shaped olefin-based molded product is deformed by an external force at a temperature lower than the primary shaped glass transition temperature or higher and fixed at a temperature lower than the glass transition temperature (secondary When the olefinic molded product retains the shape of the secondary shaping at a temperature below the glass transition temperature and is heated to a temperature above the glass transition temperature under no load, the primary shaping takes place. It means the property of returning to the shape of the shape (recovering).
  • the shape memory action can be confirmed by, for example, recovering the olefin-based molded product after being deformed and kept in a deformed state at a predetermined temperature and comparing the shape after the recovery with that before the deformation. Specifically, it can be confirmed by, for example, the method described in Examples below.
  • the shape fixing rate and shape recovery rate indicating the shape memory performance can be calculated by a change in elongation rate by thermomechanical analysis (TMA).
  • the elongation rate E2 immediately after deformation at a temperature equal to or higher than Tg It can be calculated as a ratio (E2 ′ / E2) to the elongation rate E2 ′ when fixed at a temperature below Tg, and the shape recovery rate is obtained through the elongation rate E1 returning to the original shape and the above deformation and fixation.
  • it can be calculated as the ratio (E1 ′ / E1) to the elongation E1 ′ when recovered at a temperature of Tg or higher.
  • it is a value that can be calculated from the thermal analysis result. For example, in FIG.
  • the sample was heated to 50 ° C., the 100% sample was stretched, and then cooled to 0 ° C., and the sample was fixed in that state, and the shape fixing ratio was 99.5%. It shows that. Furthermore, when the tensile load was zero and the sample was recovered when heated to 50 ° C., the shape recovery rate was 99.1%.
  • One aspect of the shape memory molded article maintains a constant shape S1 at a temperature (for example, room temperature) Tu at which it is used, and exceeds a temperature exceeding Tg (Tu ⁇ Tg) (and below the melting point if having a melting point).
  • Tg Tu ⁇ Tg
  • Td Tg
  • Tr Tr may be the same as or different from Td
  • the shape memory molded article of the above aspect can be easily deformed into a shape S2 different from the original shape S1 by applying an external force at a temperature Td exceeding Tg (Tu ⁇ Tg), and if cooled to Tu,
  • One embodiment of a molded article having shape memory properties is a copolymer having structural units represented by the above formulas (III) and (IV), respectively, and the Tg thereof is the use temperature (for example, the use temperature is room temperature).
  • the shape fixing rate and the shape recovery rate can each achieve 50% or more, and preferably each can achieve 80% or more.
  • the polar olefin polymer contained in the olefin-based molded article of the present invention has a wide glass transition temperature range, and has various mechanical properties (hard plastic, soft, depending on the glass transition temperature at room temperature (for example, 25 ° C.). Plastics, elastomers and stress softening materials). For example, as described in Examples below, P5 at a glass transition temperature of 6 ° C., P7 at 4 ° C., and P8 at 11 ° C. are elastomers at room temperature (A in FIG. 33). This elastomer exhibits excellent mechanical properties and is particularly excellent in toughness, tensile strength and elongation at break.
  • the toughness value of the olefin-based molded article is determined according to the type of polymer used (more specifically, in the embodiment including a copolymer having a structural unit represented by each of the above formulas (III) and (IV)). ) In benzene ring, and the range of x and y, and molecular weight), etc., and is not limited. Depending on the application, it can be adjusted to an appropriate range. When a polar olefin polymer having a large molecular weight (Mn) is used as a raw material, the toughness value of the obtained molded product tends to increase.
  • Mn molecular weight
  • the molded article of the present invention usually exceeds 0.25 MJ / m 3 and 0.5 MJ in a measurement at a temperature equal to or higher than the glass transition temperature at which the polymer exhibits a rubbery state (for example, room temperature (for example, 25 ° C.)). / M 3 or more can be achieved.
  • a temperature equal to or higher than the glass transition temperature at which the polymer exhibits a rubbery state for example, room temperature (for example, 25 ° C.)
  • / M 3 or more can be achieved.
  • To the self-healing of the molded article preferably, 1 MJ / m 3 or more, 5 MJ / m 3 or more, 10 MJ / m 3 or more, 20 MJ / m 3 or more, or 30 MJ / m 3 or more.
  • room temperature but the aspect which shows the toughness of the said range may be sufficient in the use temperature where the molded article is used.
  • the tensile strength of the olefin-based molded article is determined according to the type of polymer used (more specifically, in the embodiment including a copolymer having a structural unit represented by each of the above formulas (III) and (IV)). ) In benzene ring, and the range of x and y, and molecular weight), etc., and is not limited. Depending on the application, it can be adjusted to an appropriate range. When a polymer having a high glass transition point is used as a raw material, the tensile strength of the molded product tends to increase.
  • the molded article of the present invention can achieve about 0.1 MPa or more in measurement at a temperature higher than the glass transition temperature at which the polymer exhibits a rubbery state (for example, room temperature (for example, 25 ° C.)).
  • a temperature higher than the glass transition temperature at which the polymer exhibits a rubbery state for example, room temperature (for example, 25 ° C.)
  • it is more than 0.4 MPa, 0.5 MPa or more, 1 MPa or more, 10.0 MPa or more, 20 MPa or more, 30 MPa or more, 40 MPa or more, or 50 MPa or more.
  • room temperature not only room temperature but the aspect which shows the tensile strength of the said range may be sufficient in the use temperature where the molded article is used.
  • the elongation at break of the olefin-based molded article is determined according to the type of polymer used (more specifically, in the embodiment including the copolymer having the structural unit represented by each of the above formulas (III) and (IV), ) In benzene ring, and the range of x and y, and molecular weight), etc., and is not limited. Depending on the application, it can be adjusted to an appropriate range. When a polymer having a high glass transition point is used as a raw material, the elongation at break of the molded product tends to be small.
  • the molded article of the present invention can achieve about 10% or more in measurement at a temperature not lower than the glass transition temperature at which the polymer exhibits a rubbery state (for example, room temperature (for example, 25 ° C.)).
  • a temperature not lower than the glass transition temperature at which the polymer exhibits a rubbery state for example, room temperature (for example, 25 ° C.)
  • room temperature for example, 25 ° C.
  • the upper limit is about 10000%.
  • room temperature not the aspect which shows the breaking elongation of the said range may be sufficient in the use temperature where the molded article is used.
  • the mechanical properties of the polar olefin polymer can be measured by a conventional tensile test. Specifically, for example, the method described in the examples below (a dumbbell-shaped test piece (width: 2251mm; length: 12 mm; thickness: 1 mm) based on JIS K-6251-7)
  • the rupture stress-breaking strain test is determined by fracture using a uniaxial tensile test at a strain rate of 200 mm / min, and the toughness value is calculated by calculating the area of the stress-strain curve. Can be calculated.
  • the olefin-based molded product of the present invention may be an olefin-based molded product containing a polar olefin polymer as a main component (50% by mass or more), or an olefin-based molded product containing a subcomponent (less than 50% by mass). There may be.
  • Polymer materials such as (co) polymers other than polar olefin polymers, and various additives usually used in molded products, such as excipients, lubricants, ultraviolet absorbers, weathering agents, antistatic agents, antioxidants Agents, heat stabilizers, nucleating agents, flow improvers, colorants, and the like.
  • the olefin-based molded product of the present invention is preferably a melt-molded polar olefin polymer.
  • the melt molding can be performed by a known method.
  • a melt-molded product is not limited, and is, for example, an injection-molded product, a vacuum, a pressure-molded product, an extrusion-molded product, a blow-molded product, a hot press (melt-pressed) molded product, a cast molded product, and the like. Examples include pellets, fibers and cloth, films, sheets, and nonwoven fabrics.
  • the molded product can be manufactured using laser processing, 3D printer technology, and the like.
  • the present invention also relates to a film containing the polar olefin polymer.
  • One embodiment of the film is a transparent film.
  • the film which is the olefin-based molded product of the present invention can be molded by a known method.
  • a molding technique such as extrusion molding, hot press molding, or cast molding can be used.
  • the molten film material can be extruded by using an extruder equipped with a T die, a circular die or the like, and further stretched and heat-treated as desired.
  • hot press molding the molten film material can be pressed and cooled using a hot plate press or the like, and further stretched and heat treated as desired.
  • an unstretched film can be cast by dissolving, casting, and drying and solidifying using a co-solvent of the film material, and further stretched and heat-treated as desired.
  • the formed unstretched film can be used as it is.
  • a material obtained by previously melt-kneading the polar olefin polymer and the above-mentioned various additives can be used, and the film material can be formed through melt-kneading at the time of forming.
  • Unstretched film can be uniaxially stretched longitudinally in the direction of mechanical flow and transversely uniaxially stretched in the direction perpendicular to the direction of mechanical flow. Simultaneous biaxial stretching by roll and tenter stretching, and tenter stretching.
  • a biaxially stretched film can be produced by stretching by a method, a biaxial stretching method by tubular stretching, or the like. Further, the film can be usually heat-set after stretching for suppressing heat shrinkability and the like.
  • the obtained film may be subjected to surface activation treatment or the like by a known method if desired.
  • molding as an elongate film you may store and convey in the state wound by roll shape.
  • the film of the present invention may be used as a molded product as it is, or may be used in combination with other types of films. Examples of combinations include combinations with other types of films, such as laminates and laminates. Or the combination with the other molded article by coating etc. can be illustrated.
  • FIG. 36B schematically shows the state of the polymer in the molded product (for example, a film) of the present invention.
  • the curve shows an alternating chain of polar olefinic monomer (A) such as anisylpropylene and nonpolar olefinic monomer (B) such as ethylene-(A) -alt- (B)- Represents a crystalline nanodomain formed by a homopolymerization sequence of a nonpolar olefin monomer (B) such as ethylene (B)-(B)-.
  • the short-chain-(B)-(B) -segments present in the copolymer according to the present invention are aggregated in a molded product (for example, a film) to form a large number of crystalline nanodomains. Conceivable. This can be understood from the fact that an X-ray diffraction peak attributed to the orthorhombic crystal (110) plane is generated by the measurement of WAXD. As a mechanism in which the molded article of the present invention exhibits a unique self-healing property, it is assumed as follows.
  • crystalline nanodomains are distributed in a matrix of flexible alternating chains (-(A) -alt- (B)-), and the crystalline nanodomains are It is thought that it functions as a physical cross-linking point that connects flexible alternating sequence chains (-(A) -alt- (B)-).
  • the crystalline nanodomains reaggregate to cause the alternating sequence chain (-(A) -alt- It is considered that the network structure (B)-) is easily reconstructed and the repair of the damaged portion is in progress.
  • the present invention also relates to a coating composition containing at least one of the (co) polymers according to the present invention.
  • the coating composition can be used to form films on various surfaces.
  • the coating composition may contain a liquid (either water-based or organic solvent-based) or a solid medium together with the polymer.
  • the polymer may be dissolved in the medium or in an undissolved (for example, dispersed) state.
  • the coating composition is applied to at least a part of the surface of the article, and if necessary, dried to remove the medium to form a film, thereby forming a film on part or all of the surface of the article.
  • the performance derived from the said polymers, such as, can be provided.
  • Metallocene complex used in the examples was synthesized according to the method described in the following literature. (1) X. Li, M. Nishiura, K. Mori, T. Mashiko, Z. Hou, Chem. Commun. 4137-4139 (2007) (2) F. Guo, M. Nishiura, H. Koshino, Z. Hou, Macromolecules. 44, 6335-6344 (2011).
  • the metallocene complexes used in the examples are as follows.
  • Complex 1 (C 5 H 5 ) Sc (CH 2 C 6 H 4 NMe 2 -o) 2
  • Complex 2 (C 5 Me 4 SiMe 3 ) Sc (CH 2 C 6 H 4 NMe 2 -o) 2
  • the structure of the metallocene complex used in the examples is shown in FIG.
  • NMR ⁇ Measurement method>
  • the NMR data of the polymer was measured using a Bruker AVANCE III HD 500 NMR (FT, 500 MHz: 1 H; 125 MHz: 13 C) spectrometer, CD 2 Cl 2 (26.8 ° C.) or 1,1,2,2-C 2 D 2 Cl 4 (120 ° C.) was used as a solvent and measured.
  • 1 H NMR measurement was performed using tetramethylsilane (TMS) as an internal standard, and chemical shifts of various solvents were as follows (7.26 ppm: CDCl 3 , 7.16 ppm: C 6 D 6 , 5.32 ppm: CD 2 Cl 2 , 6.0 ppm: 1,1,2,2-C 2 D 2 Cl 4 ).
  • DSC Different scanning calorimetry
  • the copolymer film was produced by being melt-pressed at 160 ° C. for 5 minutes under a pressure of 30 MPa and cooled to 22 ° C. at 10 ° C./hour.
  • ⁇ Tensile test> The mechanical tensile stress test was performed using an Instron 3342 instrument (Instron). Three samples were tested for each polymer composition. The tensile test was performed at room temperature (25 ⁇ 1 ° C) and ASTM 882-09 using dumbbell-shaped test pieces (width: 2 mm; length: 12 mm; thickness: 1 mm) based on JIS K-6251-7 (When evaluating stretchability, it was performed with different sample sizes and strain rates). The breaking stress-breaking strain test was determined by fracture using a uniaxial tensile test at a strain rate of 200 mm / min.
  • the Young's modulus was calculated from the average of three monotone curves, with an initial slope in the linear region (0 ⁇ ⁇ 0.05) in the nominal stress-notarized strain curve.
  • the toughness value was calculated by calculating the area of the stress-strain curve.
  • ⁇ Self-repair test> As a self-healing test, the samples were cut into completely separate sites using a razor blade. The fractured surfaces of the film were bonded in air, water, aqueous HCl and NaOH with different durations. That is, the cut surfaces were combined, lightly pressed for approximately 15 seconds, and then repaired at 25 ° C. for each time. For the restored copolymer film, a stress-strain curve was obtained by the above method. The mechanical repair efficiency ⁇ was determined as the ratio of the repair fracture strain to the original fracture strain.
  • each copolymer is schematically shown only by the alternating AP-E sequence which is the main sequence. Further, the copolymer (P1-P5) was amorphous and had a glass transition temperature. In addition, it can be estimated that the reason why the copolymer having the above specific structure was obtained by the complex 2 was that the copolymerization proceeded according to the following scheme. In the following scheme, the counter anion [B (C 6 F 5 ) 4 ] ⁇ was omitted.
  • Example 2 Physical properties of E-AP copolymer (P1-P5) A film was prepared using the copolymer P1-P5. The measurement results of the physical properties of the obtained film are shown in Table 2 and FIGS.
  • the E-AP copolymer P1-P5 could be processed into a highly transparent film with a maximum of 85% in the visible region by melting and pressing (FIG. 7).
  • the molecular weight of each copolymer significantly affected the mechanical properties (Table 2 and FIG. 8A).
  • the copolymer P1 had a relatively small number average molecular weight, exhibited stress softening after stretching by 600% at a speed of 200 mm min ⁇ 1 , and exhibited the behavior of a soft viscoelastic material (A in FIG. 8).
  • copolymer P5 showed 6% residual strain in the first cycle in the 1000% elongation stress-strain test, 9% residual strain in the 10th cycle, and excellent fatigue resistance (Fig. 8). B). Using copolymer P5 as a sample, a completely recovered stress-strain curve was obtained after 3 hours of rest after 1 cycle of 1000% elongation and release (FIG. 8C).
  • the AP R as a monomer, alternating ethylene - substituted 2-allyl anisole (E-AP R) copolymer product was obtained.
  • High molecular weight copolymers P6 to P11 were obtained using 2000 equivalents or 5000 equivalents of anisylpropylene. Copolymers P6 to P11 exhibited a wide range of glass transition temperatures depending on the various substitution components of the anisyl moiety. Increase in yield and molecular weight was confirmed by increasing the monomer complex ratio and reaction time.
  • the copolymer (P6-P11) has an alternating AP R -E sequence (about 57-78%) by 13 C ⁇ 1 H ⁇ NMR analysis, and some AP R It was shown to have-(E) n-AP R sequence (n ⁇ 2, about 20-43%) and E-AP R -AP R -E sequence (0-4%).
  • each copolymer only alternate AP R -E sequence is the main sequence is shown schematically.
  • Example 4 Physical properties of E-AP R copolymer (P6-P11) A film was prepared using the copolymer P6-P11. The measurement results of the physical properties of the obtained film are shown in Table 4 and FIGS. The films of the copolymers P6 to P11 exhibited various mechanical properties due to the wide Tg width of the copolymers P6 to P10 (A in FIG. 33). The n-hexyl copolymer P6 is a stress softening material and could be extended to 10,000% without breaking. The fluorocopolymer and methyl copolymers P7 and P8 are typical elastomers.
  • P7 and P8 showed significantly higher initial elastic modulus and tensile strength than P1 to P5 (Table 2, 4, A in FIG. 33). Although the elongation at break of P7 and P8 is shorter than P5 (Table 4), these two elastomers have higher toughness than P5, indicating that P7 and P8 have both rigidity and toughness.
  • t-butyl copolymer P9 is a soft plastic and exhibited ductility and strain hardening when pulled at room temperature at a pulling speed of 200 mm min ⁇ 1 (Table 4).
  • Naphthyl copolymer P10 is a hard plastic at room temperature.
  • the E-AP (AP R ) copolymer exhibited excellent self-healing properties in addition to excellent elasticity (FIG. 34).
  • the two damaged portions were rapidly repaired (A in FIG. 34).
  • the repaired sample was able to extend to 1000% (50% of the original value) (B, ii in FIG. 34).
  • the longer the repair time the better the repair state.
  • the damaged part was completely repaired (B, v in FIG. 34). This is verified by observing an elongation corresponding to the elongation of the sample in the initial state, in addition to breaking another location (a location that is not a repair location).
  • the stress-strain curve of the repair sample almost overlapped with the stress-strain curve of the material in the initial state. In most cases, the only difference was elongation at break (B, C in FIG. 34).
  • P5 a higher molecular weight polymer, took longer repair time and reached 90% recovery of original elongation after 120 hours at room temperature (FIG. 34C).
  • the repair sample P5 exhibited a tensile strength as high as 6.7 MPa at 1520% elongation (C and v in FIG. 34).
  • Non-Patent Document 2 a stress softening material, showed high-speed self-healing characteristics due to its high adhesiveness (I in FIG. 34). It should be noted that the fluorocopolymer and the methyl copolymers P7 and P8 showed better repair efficiency at room temperature than P5 (J, K in FIG. 34). When the repair time was 5 days, the recovery rate of elongation at break was 86% and 87%. Of further note, the P7 and P8 samples after re-repair showed tensile stresses of 11.9 MPa and 12.6 MPa. These values are the highest reported so far as an autonomous repair material, and higher than any existing self-healing material in any initial state (Non-Patent Document 2).
  • t-Butyl copolymer P9 is a soft plastic at room temperature
  • naphthyl copolymer P10 is a hard plastic at room temperature, but both showed good elastic properties at high temperatures (data not shown). Since it has thermally specific plasticity and elasticity, it has flexibility during shape manipulation. As shown in FIG. 35, a P10 film sample of a predetermined shape expands when an external force is applied at 80 ° C., and becomes a deformed shape. When the film sample is cooled to room temperature, the deformed shape is fixed, but no external force is applied. Without re-heating to 80 ° C., it was observed that the original shape recovered almost completely. In addition, as shown in FIG.
  • the P9 film sample stretched and deformed when an external force was applied at 50 ° C, and when it was cooled to 20 ° C, the deformed shape was fixed, but no external force was applied. Instead, it was observed that the original shape was almost completely recovered in 5 seconds when placed in 50 ° C. water and heated.
  • TMA thermomechanical analysis
  • the wide-angle X-ray diffraction (WAXD) of the P5 film molded article (thickness 1 mm) produced above was measured under different temperature conditions (25 ° C., 60 ° C., 90 ° C., 120 ° C., 150 ° C.). The results are shown in FIG. As shown in FIG. 37, an X-ray diffraction peak attributed to the orthorhombic crystal (110) plane was observed at 15.26 nm ⁇ 1 . This is considered to be derived from the crystalline nanodomain formed by aggregation of the homopolymerized sequence of ethylene contained in the film. This diffraction peak was not observed at 150 ° C. This suggests that crystallinity has been lost due to melting of the crystalline nanodomain.
  • SAXS small-angle X-ray scattering
  • WAXD and SAXS measurements were made at the BL05XU beamline at SPring-8 (Japan Synchrotron Radiation Laboratory, Hyogo, Japan).
  • the X-ray wavelength was set to 0.1 nm.
  • 2D WAXD and 2D SAXS patterns were recorded by a 941 ⁇ 1043 pixel PILATUS 1M (DECTRIS, Switzerland) with a pixel size of 172 ⁇ 172 ⁇ m 2 as an X-ray detector.
  • the distance from the sample to the detector was 106 mm for WAXD and 3906 mm for SAXS. Measurements were performed under precise temperature control using a sample chamber equipped with a block heater.
  • Scattering vectors were calibrated using the peak positions of CeO 2 for WAXD and collagen for SAXS. TGA was recorded on an EXSTAR TG / DTA-6200 thermobalance (Hitachi High-Tech Science Corporation, Tokyo, Japan). The temperature rising rate was 10 ° C. min ⁇ 1 .
  • the P5 of in CH 2 Cl 2 to (0.5 mg / mL) can be solvent volatilized, to form an ultrathin film, which was used as a sample for TEM measurement.
  • TEM was measured using a JEOL model JEM-2100F / SP operated at an acceleration voltage of 200 kV.
  • a layer-separated structure with nanoscale crystalline domains dispersed in a continuous matrix was observed (A in FIG. 36).
  • a P5 film produced in the same manner as described above was processed into a bag shape.
  • a string was passed through the opening of the bag to hang it, and water was poured to half the height. Puncture the needle from the bottom of the bag (bottom filled with water) toward the top (opening) and check that the needle has entered the water filled in the bag, then move the needle in the opposite direction. Pulled out from the bag. This was about 3 seconds. The needle was completely withdrawn, but the hole at the bottom of the bag opened by the needle disappeared immediately upon repair, and no water leaked from the bag. From this, it can be understood that the molded article of the present invention exhibits self-repairing properties even when used as a member disposed at the interface between the liquid and the gas.
  • the molded product of the present invention can be used, for example, as a member for closing the wells of a microplate in which a plurality of wells are arranged, and the inside of the well is sealed by using the molded product of the present invention. It can be understood that even a sample (including a liquid sample) can be injected into and taken out from the well.
  • the P5 polymer was processed and molded by a vacuum heating press into a square column shape having a length and width of 2 cm and a thickness of 5 mm.
  • This molded product sample was completely cut with a cutter in the vicinity of a length of 1 cm (intermediate point) from the end (the thickness and the vertical length were kept as they were, and the two horizontal parts were halved).
  • the cut surfaces of the two parts were pressed together by hand at room temperature, they were bonded together.
  • the upper and lower portions of the integrated sample were sandwiched between clips, the upper clip was held, and the adhesive surface was suspended substantially parallel to the floor surface. A weight of 1.2 kg was hung on the lower clip and observed for about 1 minute.
  • the bonded molded product was maintained without being separated.
  • a solution obtained by dissolving a P5 polymer in toluene is applied to a metal surface and dried to remove toluene.
  • a film can be formed on the metal surface.
  • the present invention by adjusting the molecular weight of the polar olefin polymer used as a raw material, the monomer type, the copolymerization ratio, etc., high transparency, high elasticity, self-healing characteristics, shape memory characteristics, etc. A molded product having the above functions can be obtained. According to the present invention, it is possible to provide a molded article useful for various future application fields (such as a self-repairable implant for a human body).
  • the olefin-based molded product of the present invention is not limited, but can be used for various industries (for example, medical, construction, transportation, electronics / electricity, etc.), surface coating materials, equipment, parts, products and the like.
  • the present invention can be used particularly suitably for fields in which damage is difficult to detect or costly or impossible to repair, for example, devices on the seabed, devices / medical materials, and devices in outer space.

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JP7560048B2 (ja) 2020-08-24 2024-10-02 佐藤歯材株式会社 歯科用根管長測定器具
WO2025146827A1 (ja) * 2024-01-05 2025-07-10 国立研究開発法人理化学研究所 蛍光自己修復性材料

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CN119638893B (zh) * 2024-12-26 2025-11-25 东北师范大学 一种具有自修复功能的极性3,4-异戊胶及其制备方法

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