WO2018098807A1 - 发泡结构体 - Google Patents

发泡结构体 Download PDF

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Publication number
WO2018098807A1
WO2018098807A1 PCT/CN2016/108378 CN2016108378W WO2018098807A1 WO 2018098807 A1 WO2018098807 A1 WO 2018098807A1 CN 2016108378 W CN2016108378 W CN 2016108378W WO 2018098807 A1 WO2018098807 A1 WO 2018098807A1
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Prior art keywords
foamed structure
present disclosure
wrinkle
supercritical fluid
structure according
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PCT/CN2016/108378
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English (en)
French (fr)
Inventor
罗振寰
蔡雄雄
刘伏奇
Original Assignee
东莞海锐思高分子材料科技有限公司
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Application filed by 东莞海锐思高分子材料科技有限公司 filed Critical 东莞海锐思高分子材料科技有限公司
Priority to CN201680004057.6A priority Critical patent/CN107001679B/zh
Priority to PCT/CN2016/108378 priority patent/WO2018098807A1/zh
Priority to US15/542,728 priority patent/US20180273715A1/en
Publication of WO2018098807A1 publication Critical patent/WO2018098807A1/zh

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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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3469—Cell or pore nucleation
    • B29C44/348—Cell or pore nucleation by regulating the temperature and/or the pressure, e.g. suppression of foaming until the pressure is rapidly decreased
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/35—Component parts; Details or accessories
    • B29C44/355—Characteristics of the foam, e.g. having particular surface properties or structure
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    • C08J9/228—Forming foamed products
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    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/007—Hardness
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    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • 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
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    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Definitions

  • the present disclosure relates to a foamed structure, and more particularly, to a wrinkle-free foam having a single hardness or multiple hardness.
  • foaming materials are mostly made of two-component polyurethane (PU), rubber, ethylene vinyl acetate (EVA), polyethylene (PE), polyolefin elastomer (POE), and styrene copolymer (SBS or SEBS). It is formed by one or two cross-linking foaming.
  • PU polyurethane
  • EVA ethylene vinyl acetate
  • PE polyethylene
  • POE polyolefin elastomer
  • SEBS styrene copolymer
  • foaming materials have been prepared using supercritical fluid technology such as supercritical carbon dioxide technology, supercritical nitrogen technology, and the like.
  • supercritical fluid technology is characterized by clean and environmentally friendly, it is inefficient to produce and is difficult to industrialize in large-scale production due to the need to use high pressure and/or high temperature equipment such as autoclaves.
  • the foamed structure obtained by such a supercritical technique has problems such as difficulty in controlling the foaming rate and insufficient resilience, and the size of the obtained foamed structure cannot be completely controlled, so the product needs to be refined. Process to get the final size.
  • this supercritical fluid technology still requires the use of an adhesive in the preparation of a double hardness product, thereby causing problems such as environmental pollution and inability to achieve 100% recovery.
  • the present disclosure provides a novel foamed structure that addresses one or more deficiencies that are still present in the art.
  • a wrinkle-free foamed structure having an average rebound coefficient of greater than 45% measured by the ASTM D-2632 method and having less than or equal to 99 Average pore size of ⁇ m.
  • the non-pleated foamed structure has an average rebound resilience coefficient of 50% or more as measured by the ASTM D-2632 method, and has an average pore diameter of 35 ⁇ m to 55 ⁇ m. .
  • the wrinkle-free foam structure has a specific gravity of 0.1 to 0.7 as measured by the ASTM D-297 method.
  • the non-pleated foam structure has a specific gravity of 0.17 to 0.65 as measured by the ASTM D-297 method.
  • the non-pleated foamed structure has a single hardness or a double hardness, and the hardness is 10 to 80 each according to a Shore hardness test tested by the ASTM D-2240 method. According to another embodiment of the present disclosure, the hardness is from 35 to 68 each measured by the Shore hardness test by the ASTM D-2240 method. According to still another embodiment of the present disclosure, the foamed structure has an expansion ratio of 1.4 to 1.7.
  • the non-pleated foamed structure when the non-pleated foamed structure is deformed by compression or torsion, when the deformation amount reaches 10-20%, different degrees of wrinkles are generated, and when the deformation reaches 50%, the external force is maintained for 10 seconds. Released after the clock, the folds disappeared within 0-600 seconds.
  • the deformation-free deformation when the deformation-free deformation is 10-20%, the wrinkle-free foamed structure generates different degrees of wrinkles, and when the deformation reaches 50%, the external force is maintained. After 3 seconds of release, the wrinkles disappear within 1 second.
  • the non-pleated foamed structure is produced by supercritical fluid foaming of one or more thermoplastic materials selected from the group consisting of polyurethane, rubber, ethylene-vinyl acetate, and poly An olefin, a polystyrene copolymer, a polyvinyl chloride, a polyethylene terephthalate, a thermoplastic acrylate, and any combination thereof, the supercritical fluid being selected from the group consisting of carbon dioxide, water, methane, ethane, ethylene, propylene, Methanol, ethanol, acetone, nitrogen, and combinations thereof.
  • thermoplastic materials selected from the group consisting of polyurethane, rubber, ethylene-vinyl acetate, and poly An olefin, a polystyrene copolymer, a polyvinyl chloride, a polyethylene terephthalate, a thermoplastic acrylate, and any combination thereof
  • the supercritical fluid being selected from the group consisting of carbon dioxide, water, methan
  • the supercritical fluid is selected from the group consisting of carbon dioxide, nitrogen, and combinations thereof
  • the thermoplastic material is a thermoplastic polyurethane material represented by Formula 1 below:
  • R 1 and R 2 are each independently selected from substituted or unsubstituted straight or branched C 1-12 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted straight or branched C 1 - 12 alkylphenyl, substituted or unsubstituted linear or branched C 1-12 ether group, substituted or unsubstituted linear or branched C 1-12 alkylhydroxy group, substituted or unsubstituted straight or branched chain a C 1-12 alkoxy group or a substituted or unsubstituted linear or branched C 3-12 cycloalkoxy group, wherein n is an arbitrary integer of 150 or less.
  • the use of the non-pleated foamed structure in sports equipment, packaging materials, and shoe materials is provided.
  • FIG. 1 is a flow chart of a method of preparing a foamed structure in accordance with an embodiment of the present disclosure
  • FIG. 2 is a top plan view of a foamed structure in accordance with an embodiment of the present disclosure
  • FIG. 3 is a cross-sectional view of a foamed structure in accordance with an embodiment of the present disclosure
  • FIG. 4 is a cross section of a foamed structure in accordance with an embodiment of the present disclosure.
  • FIG. 5 is a diagram of an apparatus for preparing a thermoplastic material prototype into a foamed structure, in accordance with an embodiment of the present disclosure
  • Fig. 5 frame-1; injection mechanism-2; shotgun-21; adapter-22; injection line rail-23; lower tray-24; rotary seat-25; upper tray-26; -3; upper mold-31; middle mold-32; lower mold-33; open mold mechanism-4; lift cylinder-41; shift mold cylinder-42; open mold cylinder-43; crank assembly-44.
  • first, second, etc. may be used herein to describe various elements, these elements are not limited by these terms. These terms are used to distinguish one element from another. Accordingly, the first temperature, pressure, supercritical fluid, and the like, as used hereinafter, may be referred to as a second temperature, pressure, supercritical fluid, or the like without departing from the teachings of the present disclosure.
  • clinding refers to an unfoamed structure that corresponds to the shape of the finished product and that is smaller in three dimensions.
  • supercritical fluid refers to a fluid whose temperature and pressure reach a certain critical point, and a fluid that sometimes reaches a certain critical point of temperature or pressure is referred to as a supercritical fluid.
  • a supercritical fluid Generally, the physical properties of a supercritical fluid are between gas and liquid phase, and have the advantages of low viscosity/high density/high diffusion coefficient/high organic solubility.
  • the term “foamed structure” refers to a three-dimensional body having a porous structure obtained by a foaming process, and generally used beads, microparticles, and the like are not included in the scope of the term.
  • thermoplastic polyurethane refers to diisocyanate molecules such as diphenylmethane diisocyanate (MDI) or toluene diisocyanate (TDI) and macropolyols, low molecular weight polyols (chain extenders). A polymer material obtained by co-reacting polymerization.
  • C 1-12 refers to a carbon atom having any integer number in the range of from 1 to 12 in the backbone of the group, for example 1, 2, 3, 4, 5, 6, 7, 8 9, 10, 11 or 12 carbon atoms.
  • substituted refers to a substitution using a C 1-30 alkyl group, such as a C 1-10 alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl.
  • C 6-30 aryl such as C 6-18 aryl, such as phenyl, naphthyl, hydrazine Phenyl, terphenyl or the like
  • C 1-30 alkoxy (-OA 1 ), wherein A 1 is C 1-30 alkyl as defined herein, for example C 1-10 alkoxy; C 1-30 alkane Hydroxy (-A 2 OH) wherein A 2 is C 1-30 alkyl as defined herein, eg, C 1-10 alkylhydroxy;
  • C 3-30 cycloalkyl eg, C 3-10 cycloalkyl, such as a ring a propyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloh
  • a method of preparing a foamed structure includes: providing a prototype prepared from one or more thermoplastic materials, the prototype having a corresponding shape of the foamed structure; Determining the first supercritical fluid at a first temperature and a first pressure; optionally, subjecting the first supercritical fluid to a second supercritical fluid at a second temperature And performing a second treatment under a second pressure; and foaming the obtained prototype into a structure of a predetermined shape and size.
  • the first temperature and the second temperature may be the same or different from each other.
  • the first temperature and the second temperature may each be 30 ° C to 200 ° C.
  • the first temperature and the second temperature may each be 50 ° C to 180 ° C.
  • the first temperature and the second temperature may each be from 70 °C to 160 °C.
  • the first temperature and the second temperature may each be from 90 ° C to 150 ° C.
  • the first temperature and the second temperature may each be 120 ° C to 140 ° C.
  • the first pressure and the second pressure may be the same or different from each other.
  • the first pressure and the second pressure may each be 5 MPa to 60 MPa.
  • the first pressure and the second pressure may each be 6 MPa to 55 MPa.
  • the first pressure and the second pressure may each be 7 MPa to 50 MPa.
  • the first pressure and the second pressure may each be 12 MPa to 34 or 35 MPa.
  • the first pressure and the second pressure may each be 15 MPa to 20 MPa.
  • the first supercritical fluid and the second supercritical fluid may be the same or different from each other.
  • the first supercritical fluid and the second supercritical fluid may each be selected from the group consisting of carbon dioxide, water, methane, ethane, ethylene, propylene, methanol, ethanol, acetone, nitrogen, and combination.
  • the first supercritical fluid and the second supercritical fluid may each be carbon dioxide, nitrogen, or a combination thereof.
  • the first supercritical fluid and the second supercritical fluid treatment may each be performed at a fluid pressure of 5 MPa to 60 MPa. According to still another embodiment of the present disclosure, the first supercritical fluid and the second supercritical fluid treatment may be performed at respective fluid pressures of 6 MPa to 55 MPa. According to other embodiments of the present disclosure, the first supercritical fluid and the second supercritical fluid treatment may be performed at a fluid pressure of 7 MPa to 50 MPa each. According to another embodiment of the present disclosure, the first supercritical fluid and the second supercritical fluid treatment may be performed at fluid pressures of 12 MPa to 34 MPa or 35 MPa each. According to yet another embodiment of the present disclosure, the The first supercritical fluid and the second supercritical fluid treatment may be performed at respective fluid pressures of 15 MPa to 20 MPa.
  • the fluid pressure of the first supercritical fluid may be the same as the first pressure.
  • the fluid pressure of the second supercritical fluid may be the same as the second pressure.
  • the fluid pressure of the first supercritical fluid may be different from the first pressure.
  • the fluid pressure of the second supercritical fluid may be different from the second pressure.
  • the first supercritical fluid and the second supercritical fluid may each have a fluid temperature of 50 ° C to 220 ° C. According to another embodiment of the present disclosure, the first supercritical fluid and the second supercritical fluid may each have a fluid temperature of 70 ° C to 200 ° C. According to still another embodiment of the present disclosure, the first supercritical fluid and the second supercritical fluid may each have a fluid temperature of 90 ° C to 180 ° C. According to another embodiment of the present disclosure, the first supercritical fluid and the second supercritical fluid may each have a fluid temperature of 120 ° C to 160 ° C. According to still another embodiment of the present disclosure, the first supercritical fluid and the second supercritical fluid may each have a fluid temperature of 140 ° C to 150 ° C.
  • the fluid temperature of the first supercritical fluid may be the same as the first temperature.
  • the fluid temperature of the second supercritical fluid may be the same as the second temperature.
  • the fluid temperature of the first supercritical fluid may be different from the first temperature.
  • the fluid temperature of the second supercritical fluid may be different from the second temperature.
  • the first supercritical fluid and the second supercritical fluid may each be held for 5 minutes to 1 hour. According to an embodiment of the present disclosure, the first supercritical fluid and the second supercritical fluid may each be held for 10 minutes to 50 minutes. According to still another embodiment of the present disclosure, the first supercritical fluid and the second supercritical fluid may each be held for 15 minutes to 40 minutes. According to other embodiments of the present disclosure, the first supercritical fluid and the second supercritical fluid may each be held for 20 minutes to 30 minutes.
  • the first treatment may be performed after a temperature of 90 ° C to 180 ° C, a pressure of 10 MPa to 40 MPa, for 10 minutes to 50 minutes, and then optionally cooled to 50 ° C or below.
  • the first treatment may be performed after a temperature of 100 ° C to 150 ° C, a pressure of 10 MPa to 40 MPa, for 20 minutes to 30 minutes, and then optionally cooled to 30 ° C or below.
  • the second treatment may be performed under conditions of 50 ° C to 180 ° C and a pressure of 10 MPa to 60 MPa for 15 to 40 minutes.
  • the second treatment may be performed under conditions of 90 ° C to 160 ° C and a pressure of 10 MPa to 60 MPa for 15 to 40 minutes.
  • the thermoplastic material may be selected from the group consisting of polyurethane, rubber, ethylene-vinyl acetate, polyolefin, polystyrene copolymer, polyvinyl chloride, polyethylene terephthalate, thermoplastic acrylic acid. Ester and any combination thereof.
  • the thermoplastic material may be a thermoplastic polyurethane material represented by the following formula 1:
  • R 1 and R 2 may each independently be selected from a substituted or unsubstituted linear or branched C 1-12 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted straight chain or branched chain C 1 -12 alkylphenyl, substituted or unsubstituted linear or branched C 1-12 ether group, substituted or unsubstituted linear or branched C 1-12 alkylhydroxy group, substituted or unsubstituted straight chain or branch a C 1-12 alkoxy group or a substituted or unsubstituted linear or branched C 3-12 cycloalkoxy group, wherein n may be any integer less than or equal to 150, and
  • the substituent of a straight or branched C 1-12 alkoxy group, a substituted straight or branched C 1-12 alkoxy group or a substituted straight or branched C 3-12 cycloalkoxy group may be C 1- 30 alkyl, C 1-18 alkyl, C 1-12 alkyl or C 1-6 alkyl; C 5-30 aryl, C 6-18 aryl, C 6-12 aryl or phenyl; C 1-30 alkoxy, C 1-18 alkoxy, C 1-12 alkoxy or C 1-6 alkoxy; C 1-30 alkoxy, C 1-18 alkoxy, C 1-12 alkane Hydroxy or C 1-6 alkoxy; C 3-30 cycloalkyl, C 3-18 cycloalkyl, C 3-12 cycloalky
  • the above substituent may be: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl; phenyl, biphenyl, terphenyl; Methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy; methyl hydroxy, ethyl hydroxy, propyl hydroxy, butyl hydroxy, pentyl hydroxy, hexyl hydroxy; cyclopropyl , cyclopentyl, cyclohexyl; cyclopropoxy, cyclopentyloxy, cyclohexyloxy, but is not limited thereto.
  • the prototype may be produced by injection molding, extrusion molding, hot press molding, or mold molding. According to another embodiment of the present disclosure, the prototype may be produced by injection molding.
  • the foamed structure is made from one or more thermoplastic materials by supercritical fluid foaming. According to an embodiment of the present disclosure, the foamed structure is obtained by foaming a thermoplastic polyurethane material by supercritical fluid. According to an embodiment of the present disclosure, the foamed structure is obtained by foaming a thermoplastic polyurethane material represented by Formula 1 with supercritical carbon dioxide or supercritical nitrogen.
  • a method of preparing a foamed structure directly obtains a structure of a predetermined shape and size by foaming the first processed prototype without a subsequent finishing step.
  • a method of preparing a foamed structure directly obtains a structure of a predetermined shape and size by foaming the second processed preform without a subsequent finishing step.
  • the first process and the second process are performed in the same mold. According to another embodiment of the present disclosure, the first process and the second process are performed in different molds. According to still another embodiment of the present disclosure, the first (or second) processed crepe is foamed into a structure of a predetermined shape and size depending on the shape and size of the mold.
  • the methods of making a foamed structure described herein can be used to directly fabricate sports equipment, including materials, and shoe materials. According to another embodiment of the present disclosure, the method of making a foamed structure described herein can be used to directly obtain a sole without subsequent processing.
  • the foamed structure is a wrinkle-free foamed structure.
  • the foamed structure may have an average rebound resilience coefficient greater than 45% as measured by the ASTM D-2632 method.
  • the foamed structure may have an average rebound coefficient of 50% or more as measured by the ASTM D-2632 method, for example, 51% or more, 52% or more, and 53% or more. , greater than or equal to 54%.
  • the foamed structure may have an average rebound resilience coefficient of 55% or more as measured by the ASTM D-2632 method.
  • the foamed structure may have an average rebound resilience coefficient of 60% or more as measured by the ASTM D-2632 method.
  • the foamed structure has a single average rebound coefficient or a double average rebound coefficient, and the average rebound resilience is each greater than 45%.
  • the foamed structure has a single average rebound resilience coefficient or a double average resilience coefficient, and the average resilience coefficient is each 50% or more, for example, 51% or more and 52% or more. , greater than or equal to 53%, greater than or equal to 54% or greater than or equal to 55%.
  • the foamed structure may have an average pore diameter of 99 ⁇ m or less. According to another embodiment of the present disclosure, the foamed structure may have an average pore diameter of 35 ⁇ m to 55 ⁇ m. According to still another embodiment of the present disclosure, the foamed structure may have an average pore diameter of 45 ⁇ m to 50 ⁇ m.
  • the foamed structure may have a specific gravity of 0.7 or less as measured by the ASTM D-297 method. According to another embodiment of the present disclosure, the foamed structure may have a specific gravity of 0.1 to 0.7 as measured by the ASTM D-297 method. According to still another embodiment of the present disclosure, the foamed structure may have a specific gravity of 0.17 to 0.65 as measured by the ASTM D-297 method. According to another embodiment of the present disclosure, the foamed structure may have a specific gravity of 0.2 to 0.6 as measured by the ASTM D-297 method. According to still another embodiment of the present disclosure, the foamed structure may have a specific gravity of 0.25 to 0.55 as measured by the ASTM D-297 method.
  • the foamed structure may have a specific gravity of 0.3 to 0.5 as measured by the ASTM D-297 method. According to still another embodiment of the present disclosure, the foamed structure may have a specific gravity of 0.35 to 0.45 measured by the ASTM D-297 method.
  • the foamed structure may have a single hardness. According to another embodiment of the present disclosure, the foamed structure may have a double hardness. According to an embodiment of the present disclosure, the hardness may be 10 to 80 each in terms of Shore hardness test by the ASTM D-2240 method. According to another embodiment of the present disclosure, the hardness may be 20 to 75 each by a Shore hardness tester tested by the ASTM D-2240 method. According to still another embodiment of the present disclosure, the hardness may be 30 to 70 each by a Shore hardness tester tested by the ASTM D-2240 method. According to another embodiment of the present disclosure, the hardness may be 35 to 68 each by a Shore hardness tester tested by the ASTM D-2240 method.
  • the hardness may be 40 to 60 each by a Shore hardness tester tested by the ASTM D-2240 method. According to another embodiment of the present disclosure, the hardness may be from 42 to 55 each by a Shore hardness tester tested by the ASTM D-2240 method. According to still another embodiment of the present disclosure, the hardness may be 45 to 50 each by a Shore hardness tester tested by the ASTM D-2240 method.
  • the foamed structure may have an expansion ratio of 1.4 to 1.7.
  • the foaming structure may have an expansion ratio of 1.45 to 1.65.
  • the foamed structure may have an expansion ratio of 1.5 to 1.6.
  • the foamed structure may have an expansion ratio of 1.55.
  • the foamed structure when the foamed structure is deformed by compression or torsion, when the amount of deformation reaches 10-20%, wrinkles of different degrees are generated, and when the deformation reaches 50%, the external force is maintained for 10 seconds. Release, wrinkles disappear within 0-600 seconds.
  • different degrees of wrinkles when the foamed structure is deformed by compression or torsion, different degrees of wrinkles are generated when the amount of deformation reaches 10-20%, and when the deformation reaches 50%, the external force is maintained for 3 seconds. After release, the wrinkles disappear immediately (for example, less than 1 second).
  • the foamed structure is a foamed structure obtained by the method described herein above. According to another embodiment of the present disclosure, the foamed structure is a foamed structure obtained by other methods than those described herein.
  • the foamed structure described herein can be used in sports equipment, packaging materials, and shoe materials. According to another embodiment of the present disclosure, the foamed structure described herein can be used as a sole material.
  • thermoplastic polyurethane available from BASF under the tradenames Elastollan 1180A, 1185A, 1190A
  • thermoplastic polyester copolymer elastomer available from DuPont under the trade name Hytrel 3078.
  • thermoplastic granules are molded through an injection machine into a desired prototype having a reduced ratio of expansion ratio.
  • This prototype is then placed in a mold having the above specified temperature and brought to thermal equilibrium.
  • Supercritical carbon dioxide or nitrogen is injected into the mold, pressurized and held for a while.
  • the coolant is introduced into the mold and the supercritical carbon dioxide or nitrogen is vented.
  • the supercritical carbon dioxide or nitrogen gas may be re-introduced according to actual needs, pressurized and maintained for a period of time, thereby performing secondary infiltration, which can control the foaming of the prototype. Magnification.
  • Elastollan 1180A pellets 100 parts by weight of Elastollan 1180A pellets are placed in a feed barrel of a plastic injection machine, and then melted through the extruder screw feed, and metered and injected into a prototype mold to form a desired prototype, wherein Processing temperature: 130 ⁇ 200 ° C; prototype size: 150mm ⁇ 90mm ⁇ 3 ⁇ 10mm.
  • the prototype was placed in a mold having a temperature of 90 to 180 °C.
  • the carbon dioxide is then adjusted in the supply tank to a fluid pressure of 6.9 MPa to 34.5 MPa and a temperature of 90 to 180 ° C so that the carbon dioxide in the tank is in a supercritical fluid state.
  • the supercritical fluid inlet valve on the mold is opened, supercritical carbon dioxide is injected into the mold, and the pressure is maintained at 6.9 MPa to 34.5 MPa and maintained for 10 to 50 minutes.
  • the coolant is introduced into the mold and the supercritical fluid is discharged, so that the prototype is foamed and expanded, and the mold is opened to obtain the finished foam having the desired structure and shape.
  • Elastollan 1185A pellets 100 parts by weight of Elastollan 1185A pellets are placed in a feed barrel of a plastic injection machine, and then melted by the extruder screw feed, and metered and injected into a prototype mold to form a desired prototype, wherein Processing temperature: 130 to 200 ° C; size: 150 mm ⁇ 90 mm ⁇ 3 to 10 mm.
  • the prototype was placed in a mold having a temperature of 90 to 180 °C.
  • the carbon dioxide is then adjusted in the supply tank to a fluid pressure of 6.9 MPa to 34.5 MPa and a temperature of 90 to 180 ° C so that the carbon dioxide in the tank is in a supercritical fluid state.
  • the supercritical fluid inlet valve on the mold is opened, supercritical carbon dioxide is injected into the mold, and the pressure is maintained at 6.9 MPa to 34.5 MPa and maintained for 10 to 50 minutes.
  • the coolant is introduced into the mold and the supercritical fluid is discharged, so that the prototype is foamed and expanded, and the mold is opened to obtain the finished foam having the desired structure and shape.
  • Elastollan 1190A pellets 100 parts by weight of Elastollan 1190A pellets are placed in a feed barrel of a plastic injection machine, and then melted by the extruder screw feed, and metered, and ejected into a prototype mold to form a desired prototype, wherein Processing temperature: 130 to 200 ° C; size: 150 mm ⁇ 90 mm ⁇ 3 to 10 mm.
  • the prototype was placed in a mold having a temperature of 90 to 180 °C.
  • the carbon dioxide is then adjusted in the supply tank to a fluid pressure of 6.9 MPa to 34.5 MPa and a temperature of 90 to 180 ° C so that the carbon dioxide in the tank is in a supercritical fluid state.
  • the supercritical fluid inlet valve on the mold is opened, supercritical carbon dioxide is injected into the mold, and the pressure is maintained at 6.9 MPa to 34.5 MPa and maintained for 10 to 50 minutes.
  • the coolant is introduced into the mold and the supercritical fluid is discharged, so that the prototype is foamed and expanded, and the mold is opened to obtain the finished foam having the desired structure and shape.
  • Example 5 Foaming of a mixture of Elastollan 1180A and Elastollan 1185A
  • Elastollan 1180A granules and Elastollan 1185A granules are placed in a feeding barrel of a plastic injection machine, and then melted by the injection screw of the injection machine, and metered and injected into a prototype mold to form a desired double hardness prototype.
  • processing temperature 130 ⁇ 200 ° C
  • size 150 mm ⁇ 90 mm ⁇ 3 ⁇ 10 mm.
  • the double hardness prototype was placed in a mold having a temperature of 90 to 150 °C.
  • the carbon dioxide is then adjusted in the supply tank to a fluid pressure of 6.9 MPa to 34.5 MPa and a temperature of 90 to 150 ° C so that the carbon dioxide in the tank is in a supercritical fluid state.
  • the supercritical fluid inlet valve on the mold is opened, supercritical carbon dioxide is injected into the mold, and the pressure is maintained at 6.9 MPa to 34.5 MPa and maintained for 10 to 50 minutes.
  • the coolant is introduced into the mold and the supercritical fluid is discharged, so that the prototype is foamed and expanded, and the mold is opened to obtain the finished foam having the desired structure and shape.
  • the finished foam having the desired structure and shape was prepared in the same manner as in Example 1 according to the materials and parameters shown in Table 1 below.
  • the physical properties of the foams of the above Examples 2 to 8 were tested with reference to Table 2 below.
  • the test methods were ASTM D-2632 (rebound test), ASTM D-297 (specific gravity test), and ASTM D-2240 (hardness test).
  • the data listed in Table 2 is the average of at least three replicates.
  • the surface of the finished product is extruded by hand, and when the deformation reaches 10-20%, wrinkles of different degrees begin to appear, and when the deformation reaches 50%, the compression is maintained. After releasing the hand in seconds, the folds disappeared immediately.
  • the main component of the foamed structure is a thermoplastic polymer elastomer material, and the foaming agent is a supercritical fluid.
  • the foam of the present disclosure has high resilience, light weight, no chemical residue, is environmentally friendly, can be 100% recycled, and can have double hardness and high foaming consistency.
  • the foam structure manufacturing method of the present disclosure has the advantages of mass production, secondary processing, non-toxic environmental protection and low production cost.

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Abstract

本公开涉及一种无褶皱发泡结构体，具有以ASTM D-2632方法测得的大于45％的平均回弹性系数并且具有小于等于99μm的平均孔径。

Description

发泡结构体 技术领域
本公开涉及发泡结构体，更特别地，涉及具有单硬度或多硬度的无褶皱发泡体。
背景技术
目前，发泡材料多以两液型聚氨酯(PU)、橡胶、乙烯醋酸乙烯酯(EVA)、聚乙烯(PE)、聚烯烃弹性体(POE)以及苯乙烯共聚物(SBS或SEBS)等材料经一次或二次交联发泡而成。对于双硬度发泡结构体，则必需使用粘合剂进行上胶粘合等工序。这样的发泡材料因制备过程中需使用各类有机或无机化学发泡剂、交联剂、添加剂等，因此存在化学残留物等问题，对人体或环境产生一定程度的不良影响。通常，发泡工艺后需要多道加工程序和粘合程序，如此才能获得具有最终尺寸的单硬度或双硬度成品。
近年来，开始利用超临界流体技术(诸如超临界二氧化碳技术、超临界氮气技术等)来制备发泡材料。尽管超临界流体技术具有清洁环保的特点，但是由于需要使用诸如高压釜的高压和/或高温设备，因此生产效率较低，难以工业化大规模生产。通过这种超临界技术所制得的发泡结构体存在发泡率不易控制、回弹性不足等问题，而且所制得的发泡结构体的尺寸不能完全得到控制，因此仍需要对产品进行精加工以得到最终尺寸。此外，这种超临界流体技术在制备双硬度产品时，仍需要使用粘合剂，由此存在对环境的污染、不能实现100％回收等问题。
基于此，本公开提供了一种新颖的发泡结构体，从而解决了本领域中尚存在的一个或多个不足。
发明内容
在本公开的一方面中，提供了无褶皱发泡结构体，其具有以ASTM D-2632方法测得的大于45％的平均回弹性系数并且具有小于等于99 μm的平均孔径。根据本公开的一实施方案，所述无褶皱发泡结构体具有以ASTM D-2632方法测得的大于等于50％的平均回弹性系数，并且具有35μm至55μm的平均孔径。。
根据本公开的一实施方案，所述无褶皱发泡体结构具有以ASTM D-297方法测得的0.1至0.7的比重。根据本公开的另一实施方案，所述无褶皱发泡体结构具有以ASTM D-297方法测得的0.17至0.65的比重。
根据本公开的一实施方案，所述无褶皱发泡结构体具有单硬度或双硬度，并且所述硬度以通过ASTM D-2240方法测试的肖氏硬度计，各自为10至80。根据本公开的另一实施方案，所述硬度以通过ASTM D-2240方法测试的肖氏硬度计，各自为35至68。根据本公开的又一实施方案，所述发泡结构体的发泡倍率为1.4至1.7。
根据本公开的一实施方案，所述无褶皱发泡结构体在被压缩或扭转变形时，当变形量达到10-20％即产生不同程度的褶皱，当形变达到50％时，外力维持10秒钟后释放，褶皱在0-600秒内消失。根据本公开的另一实施方案，所述无褶皱发泡结构体在被压缩或扭转变形时，在变形量达到10-20％时即产生不同程度的褶皱，当变形达到50％时，外力维持3秒后释放，则褶皱在1秒内消失。
根据本公开的一实施方案，所述无褶皱发泡结构体由一种或多种热塑性材料经超临界流体发泡制得，所述热塑性材料选自聚氨酯、橡胶、乙烯-乙酸乙烯酯、聚烯烃、聚苯乙烯共聚物、聚氯乙烯、聚对苯二甲酸乙二醇酯、热塑性丙烯酸酯及其任意组合，所述超临界流体选自二氧化碳、水、甲烷、乙烷、乙烯、丙烯、甲醇、乙醇、丙酮、氮气及其组合。
根据本公开的另一实施方案，所述超临界流体选自二氧化碳、氮气及其组合，并且所述热塑性材料由以下式1表示的热塑性聚氨酯材料：
Figure PCTCN2016108378-appb-000001
其中，R1、R2各自独立地选自取代或未取代的直链或支链C1-12烷基、取代或未取代的苯基、取代或未取代的直链或支链C1-12烷基苯基、取代或未取代的直链或支链C1-12醚基、取代或未取代的直链或支链C1-12烷羟基、取代或未取代的直链或支链C1-12烷氧基或者取代或未取代的直链或支链C3-12环烷氧基，其中n为小于等于150的任意整数。
在本公开的另一方面中，提供了所述无褶皱发泡结构体在运动器材、包装材料以及鞋材中的用途。
附图说明
下文参考附图来进一步描述本文所例示的实施方案，但是附图仅仅是为了使本领域技术人员更好地理解本公开内容，而不限定其范围。
图1是根据本公开的一实施方案的制备发泡结构体的方法的流程图；
图2是根据本公开的一实施方案的发泡结构体的俯视图；
图3是根据本公开的一实施方案的发泡结构体的剖面图；
图4是根据本公开的一实施方案的发泡结构体的横截面；
图5是根据本公开的一实施方案的将热塑性材料雏型品制备成发泡结构体的设备的图；
在图5中：机架-1；注料机构-2；射枪-21；转接头-22；注料线轨-23；下托盘-24；旋转座-25；上托盘-26；成型模具-3；上模具-31；中模具-32；下模具-33；开拉模机构-4；上升油缸-41；移模油缸-42；开合模油缸-43；曲柄组件-44。
具体实施方式
在下文描述中，出于解释目的，阐述了多个具体细节，从而提供对各种示例性实施方案的深入理解。然而，显而易见的是，可以在没 有这些具体细节的情况下或用一个或多个等同布置来实施各种示例性实施方案。
在附图中，出于清楚和描述目的，可以放大元件的尺寸和相对尺寸，并且元件的形状仅为例示性的，而不限定本公开的实施方案。尽管术语第一、第二等在本文中可以用于描述各种要素，但这些要素不应受这些术语的限制。这些术语用于使一个要素与另一要素相区分。因此，下文所用的第一温度、压力、超临界流体等，在不背离本公开的教导的情况下，可以称为第二温度、压力、超临界流体等。
空间相对术语，例如“下方”、“之下”、“下”、“之上”、“上方”、“上”等，在本文中用于描述目的，由此用于描述一个要素与另一要素的关系，例如在附图中所例示的关系。然而，这样的空间相对术语旨在包括在使用、操作和/或制造中的装置的不同方向。例如，如果装置被翻转，则被描述成在其他要素或特征“之下”或“下方”的要素会被定位在其他要素或特征“之上”。因此，示例性术语“之下”可以包括上和下的方向两者。此外，装置可以以其他方式定向(例如，旋转90度或在其他方向上)，并且如此，本文所用的空间相对描述被相应地解释。
本文所用的术语是出于描述特定实施方案的目的，而不旨在进行限制。如本文所用，单数形式还包括复数形式，除非上下文明显另有所指。此外，术语“包含”和/或“包括”，当用于本说明书时，用于指明所述的特征、步骤、操作、元件、部件等的存在，但不排除一个或多个其他的特征、步骤、操作、元件、部件等的存在。
除非另外定义，本文使用的所有术语(包括技术术语和科学术语)均具有如本公开所属领域的普通技术人员通常理解的相同含义。术语，诸如在常用词典中定义的那些术语，应解释为具有与其在相关技术的上下文中的含义相符的含义，并且不会以理想化或过于正式的含义来解释，除非本文明确如此定义。
定义
如本文所用，术语“雏型品”是指与成品形状相对应且三维尺寸均更小的未发泡的结构体。
如本文所用，术语“超临界流体”是指温度及压力达到某一临界点的流体，有时也把温度或压力达到某一临界点的流体称为超临界流体。通常，超临界流体的物理性质是介于气、液相之间，具有低粘度/高密度/高扩散系数/高有机物溶解度等优点。
如本文所用，术语“发泡结构体”是指具有通过发泡工艺而得的多孔结构的三维体，而且通常所用的小球、微粒等并不包括在此术语的范围内。
如本文所用，术语“热塑性聚氨酯(TPU)”是指由二苯甲烷二异氰酸酯(MDI)或甲苯二异氰酸酯(TDI)等二异氰酸酯类分子和大分子多元醇、低分子多元醇(扩链剂)共同反应聚合而成的高分子材料。
如本文所用，术语“C1-12”是指基团的主链中具有1至12的范围内的任意整数值的碳原子，例如1、2、3、4、5、6、7、8、9、10、11或12个碳原子。
如本文所用，术语“取代的”是指使用下述取代基进行取代：C1-30烷基，例如C1-10烷基，诸如甲基、乙基、丙基、异丙基、丁基、仲丁基、叔丁基、戊基、己基、庚基、辛基、壬基、癸基等；C6-30芳基，例如C6-18芳基，诸如苯基、萘基、联苯基、三联苯基等；C1-30烷氧基(-OA1)，其中A1为本文所定义的C1-30烷基，例如C1-10烷氧基；C1-30烷羟基(-A2OH)，其中A2为本文所定义的C1-30烷基，例如C1-10烷羟基；C3-30环烷基，例如C3-10环烷基，诸如环丙基、环丁基、环戊基、环己基、环庚基等；C3-30环烷氧基(-OA3)，其中A3为本文所定义的C3-30环烷基，例如C3-10环烷氧基。
制备发泡结构体的方法
根据本公开的一实施方案，制备发泡结构体的方法包括：提供由一种或多种热塑性材料制备的雏型品，所述雏型品具有所述发泡结构体相应的形状；将所述雏型品以第一超临界流体在第一温度和第一压力下进行第一处理；任选地，将经第一超临界流体处理的雏型品以第二超临界流体在第二温度和第二压力下进行第二处理；以及将所得的雏型品发泡成预定形状和尺寸的结构体。
根据本公开的一实施方案，所述第一温度与所述第二温度可以彼此相同或不同。根据本公开的另一实施方案，所述第一温度及所述第二温度可以各自为30℃至200℃。根据本公开的又一实施方案，所述第一温度及所述第二温度可以各自为50℃至180℃。根据本公开的其他实施方案，所述第一温度及所述第二温度可以各自为70℃至160℃。根据本公开的另一实施方案，所述第一温度及所述第二温度可以各自为90℃至150℃。根据本公开的又一实施方案，所述第一温度及所述第二温度可以各自为120℃至140℃。
根据本公开的一实施方案，所述第一压力与所述第二压力可以彼此相同或不同。根据本公开的另一实施方案，所述第一压力及所述第二压力可以各自为5MPa至60MPa。根据本公开的又一实施方案，所述第一压力及所述第二压力可以各自为6MPa至55MPa。根据本公开的其他实施方案，所述第一压力及所述第二压力可以各自为7MPa至50MPa。根据本公开的另一实施方案，所述第一压力及所述第二压力可以各自为12MPa至34或35MPa。根据本公开的又一实施方案，所述第一压力及所述第二压力可以各自为15MPa至20MPa。
根据本公开的一实施方案，所述第一超临界流体与所述第二超临界流体可以彼此相同或不同。根据本公开的另一实施方案，所述第一超临界流体及所述第二超临界流体可以各自选自二氧化碳、水、甲烷、乙烷、乙烯、丙烯、甲醇、乙醇、丙酮、氮气及其组合。根据本公开的又一实施方案，所述第一超临界流体及所述第二超临界流体可以各自为二氧化碳、氮气或其组合。
根据本公开的一实施方案，所述第一超临界流体及所述第二超临界流体处理可以各自具有5MPa至60MPa的流体压力进行。根据本公开的又一实施方案，所述第一超临界流体及所述第二超临界流体处理可以各自6MPa至55MPa的流体压力进行。根据本公开的其他实施方案，所述第一超临界流体及所述第二超临界流体处理可以各自7MPa至50MPa的流体压力进行。根据本公开的另一实施方案，所述第一超临界流体及所述第二超临界流体处理可以各自12MPa至34MPa或35MPa的流体压力进行。根据本公开的又一实施方案，所述 第一超临界流体及所述第二超临界流体处理可以各自15MPa至20MPa的流体压力进行。
根据本公开的一实施方案，所述第一超临界流体的流体压力可以与所述第一压力相同。根据本公开的另一实施方案，所述第二超临界流体的流体压力可以与所述第二压力相同。根据本公开的一实施方案，所述第一超临界流体的流体压力可以与所述第一压力不相同。根据本公开的另一实施方案，所述第二超临界流体的流体压力可以与所述第二压力不相同。
根据本公开的一实施方案，所述第一超临界流体及所述第二超临界流体可以各自具有50℃至220℃的流体温度。根据本公开的另一实施方案，所述第一超临界流体及所述第二超临界流体可以各自具有70℃至200℃的流体温度。根据本公开的又一实施方案，所述第一超临界流体及所述第二超临界流体可以各自具有90℃至180℃的流体温度。根据本公开的另一实施方案，所述第一超临界流体及所述第二超临界流体可以各自具有120℃至160℃的流体温度。根据本公开的又一实施方案，所述第一超临界流体及所述第二超临界流体可以各自具有140℃至150℃的流体温度。
根据本公开的一实施方案，所述第一超临界流体的流体温度可以与所述第一温度相同。根据本公开的另一实施方案，所述第二超临界流体的流体温度可以与所述第二温度相同。根据本公开的一实施方案，所述第一超临界流体的流体温度可以与所述第一温度不相同。根据本公开的另一实施方案，所述第二超临界流体的流体温度可以与所述第二温度不相同。
根据本公开的一实施方案，所述第一超临界流体及所述第二超临界流体可以各自被保压5分钟至1小时。根据本公开的一实施方案，所述第一超临界流体及所述第二超临界流体可以各自被保压10分钟至50分钟。根据本公开的又一实施方案，所述第一超临界流体及所述第二超临界流体可以各自被保压15分钟至40分钟。根据本公开的其他实施方案，所述第一超临界流体及所述第二超临界流体可以各自被保压20分钟至30分钟。
根据本公开的一实施方案，所述第一处理可以包括在温度90℃至180℃、压力10MPa至40MPa的条件下进行10分钟至50分钟后，然后任选地降温至50℃或以下。根据本公开的另一实施方案，所述第一处理可以包括在温度100℃至150℃、压力10MPa至40MPa的条件下进行20分钟至30分钟后，然后任选地降温至30℃或以下。根据本公开的一实施方案，所述第二处理可以包括在50℃至180℃、压力10MPa至60MPa的条件下进行15至40分钟。根据本公开的一实施方案，所述第二处理可以包括在90℃至160℃、压力10MPa至60MPa的条件下进行15至40分钟。
根据本公开的一实施方案，所述热塑性材料可以选自聚氨酯、橡胶、乙烯-乙酸乙烯酯、聚烯烃、聚苯乙烯共聚物、聚氯乙烯、聚对苯二甲酸乙二醇酯、热塑性丙烯酸酯及其任意组合。根据本公开的又一实施方案，所述热塑性材料可以为由以下式1表示的热塑性聚氨酯材料：
Figure PCTCN2016108378-appb-000002
其中，R1、R2可以各自独立地选自取代或未取代的直链或支链C1-12烷基、取代或未取代的苯基、取代或未取代的直链或支链C1-12烷基苯基、取代或未取代的直链或支链C1-12醚基、取代或未取代的直链或支链C1-12烷羟基、取代或未取代的直链或支链C1-12烷氧基或者取代或未取代的直链或支链C3-12环烷氧基，其中n可以为小于等于150的任意整数，并且
取代的直链或支链C1-12烷基、取代的苯基、取代的直链或支链C1-12烷苯基、取代的直链或支链C1-12醚基、取代的直链或支链C1-12烷羟基、取代的直链或支链C1-12烷氧基或者取代的直链或支链C3-12环烷氧基的取代基可以是C1-30烷基、C1-18烷基、C1-12烷基或C1-6烷基；C5-30芳基、C6-18芳基、C6-12芳基或苯基；C1-30烷氧基、C1-18烷氧基、C1-12烷氧基或C1-6烷氧基；C1-30烷羟基、C1-18烷羟基、C1-12烷羟基或 C1-6烷羟基；C3-30环烷基、C3-18环烷基、C3-12环烷基、C3-6环烷基；C3-30环烷氧基、C3-18环烷氧基、C3-12环烷氧基、C3-6环烷氧基。
更具体地，上述取代基可以为：甲基、乙基、丙基、异丙基、丁基、仲丁基、叔丁基、戊基、己基；苯基、联苯基、三联苯基；甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基；甲基羟基、乙基羟基、丙基羟基、丁基羟基、戊基羟基、己基羟基；环丙基、环戊基、环己基；环丙氧基、环戊氧基、环己氧基，但不限于此。
根据本公开的一实施方案，所述雏型品可以通过射出成型、挤出成型、热压成型、铸模成型而制得。根据本公开的另一实施方案，所述雏型品可以通过射出成型而制得。
根据本公开的一实施方案，发泡结构体由一种或多种热塑性材料经超临界流体发泡制得。根据本公开的一实施方案，发泡结构体由热塑性聚氨酯材料经超临界流体发泡制得。根据本公开的一实施方案，发泡结构体由式1所示的热塑性聚氨酯材料经超临界二氧化碳或超临界氮气发泡制得。
根据本公开的一实施方案，制备发泡结构体的方法通过将经第一处理的雏型品发泡而直接获得预定形状和尺寸的结构体，而不需要后续的精加工步骤。根据本公开的另一实施方案，制备发泡结构体的方法通过将经第二处理的雏型品发泡而直接获得预定形状和尺寸的结构体，而不需要后续的精加工步骤。
根据本公开的一实施方案，第一处理和第二处理在相同的模具中进行。根据本公开的另一实施方案，第一处理和第二处理在不同的模具中进行。根据本公开的又一实施方案，第一(或第二)处理后的雏型品依模具的形状和尺寸而发泡成预定形状和尺寸的结构体。
根据本公开的一实施方案，本文所述的制备发泡结构体的方法可以用于直接制造运动器材、包括材料以及鞋材。根据本公开的另一实施方案，本文所述的制备发泡结构体的方法可以用于直接得到鞋底，而无需后续的加工。
发泡结构体
根据本公开的一实施方案，所述发泡结构体是无褶皱发泡结构体。根据本公开的一实施方案，所述发泡结构体可以具有以ASTM D-2632方法测得平均回弹性系数大于45％。根据本公开的另一实施方案，所述发泡结构体可以具有以ASTM D-2632方法测得的平均回弹性系数大于等于50％，例如大于等于51％、大于等于52％、大于等于53％、大于等于54％。根据本公开的又一实施方案，所述发泡结构体可以具有以ASTM D-2632方法测得的平均回弹性系数大于等于55％。根据本公开的其他实施方案，所述发泡结构体可以具有以ASTM D-2632方法测得的平均回弹性系数大于等于60％。
根据本发明的一实施方案，所述发泡结构体具有单一平均回弹性系数或双重平均回弹性系数，并且所述平均回弹性各自大于45％。根据本公开的另一实施方案，所述发泡结构体具有单一平均回弹性系数或双重平均回弹性，并且所述平均回弹性系数各自大于等于50％，例如大于等于51％、大于等于52％、大于等于53％、大于等于54％或大于等于55％。
根据本公开的一实施方案，所述发泡结构体可以具有小于等于99μm的平均孔径。根据本公开的另一实施方案，所述发泡结构体可以具有35μm至55μm的平均孔径。根据本公开的又一实施方案，所述发泡结构体可以具有45μm至50μm的平均孔径。
根据本公开的一实施方案，所述发泡结构体可以具有以ASTM D-297方法测得的小于等于0.7的比重。根据本公开的另一实施方案，所述发泡结构体可以具有以ASTM D-297方法测得的0.1至0.7的比重。根据本公开的又一实施方案，所述发泡结构体可以具有以ASTM D-297方法测得的0.17至0.65的比重。根据本公开的另一实施方案，所述发泡结构体可以具有以ASTM D-297方法测得的0.2至0.6的比重。根据本公开的又一实施方案，所述发泡结构体可以具有以ASTM D-297方法测得的0.25至0.55的比重。根据本公开的另一实施方案，所述发泡结构体可以具有以ASTM D-297方法测得的0.3至0.5的比重。根据本公开的又一实施方案，所述发泡结构体可以具有以ASTM D-297方法测得的0.35至0.45的比重。
根据本公开的一实施方案，所述发泡结构体可以具有单硬度。根据本公开的另一实施方案，所述发泡结构体可以具有双硬度。根据本公开的一实施方案，所述硬度以通过ASTM D-2240方法测试的肖氏硬度计，可以各自为10至80。根据本公开的另一实施方案，所述硬度以通过ASTM D-2240方法测试的肖氏硬度计，可以各自为20至75。根据本公开的又一实施方案，所述硬度以通过ASTM D-2240方法测试的肖氏硬度计，可以各自为30至70。根据本公开的另一实施方案，所述硬度以通过ASTM D-2240方法测试的肖氏硬度计，可以各自为35至68。根据本公开的又一实施方案，所述硬度以通过ASTM D-2240方法测试的肖氏硬度计，可以各自为40至60。根据本公开的另一实施方案，所述硬度以通过ASTM D-2240方法测试的肖氏硬度计，可以各自为42至55。根据本公开的又一实施方案，所述硬度以通过ASTM D-2240方法测试的肖氏硬度计，可以各自为45至50。
根据本公开的一实施方案，所述发泡结构体的发泡倍率可以为1.4至1.7。根据本公开的另一实施方案，所述发泡结构体的发泡倍率可以为1.45至1.65。根据本公开的又一实施方案，所述发泡结构体的发泡倍率可以为1.5至1.6。根据本公开的一实施方案，所述发泡结构体的发泡倍率可以为1.55。
根据本公开的一实施方案，所述发泡结构体在被压缩或扭转变形时，当变形量达到10-20％即产生不同程度的褶皱，当形变达到50％时，外力维持10秒钟后释放，褶皱在0-600秒内消失。根据本公开的另一实施方案，所述发泡结构体在被压缩或扭转变形时，在变形量达到10-20％时即产生不同程度的褶皱，当变形达到50％时，外力维持3秒后释放，则褶皱立即消失(例如，小于1秒)。
根据本公开的一实施方案，所述发泡结构体是通过本文上述的方法获得的发泡结构体。根据本公开的另一实施方案，所述发泡结构体是通过本文所述的方法之外的其他方法获得的发泡结构体。
根据本公开的一实施方案，本文所述的发泡结构体可以用于运动器材、包装材料以及鞋材中。根据本公开的另一实施方案，本文所述的发泡结构体可以用于用作鞋底材料。
实施例
提供以下实施例以说明一个或多个实施方案的特性，但应理解，实施例不应被解释为限制欲保护发明的范围。
以下实例使用：热塑性聚氨酯(TPU)，其以商品名Elastollan1180A、1185A、1190A购自巴斯夫公司；热塑性聚酯共聚弹性体(TPEE)，其以商品名Hytrel 3078购自杜邦公司。
实施例1：一般成型操作
将热塑性塑料颗粒经由射出机而成型为所需的依发泡倍率比例缩小的雏型品。然后，将此雏型品置于具有上述特定温度的模具内并使其达到热平衡。向模具内注入超临界二氧化碳或氮气，加压并保持一段时间。待超临界二氧化碳或氮气浸润入雏型品之后，向模具通入冷却液，并泄出超临界二氧化碳或氮气。通过开模泄压(一般而言，开模速度为200mm/秒以上)或加热模具，使所得的雏型品发泡，直接获得成品，该成品仅需烘烤定型即可使用，而无需后续的对尺寸和/或形状的精加工。
可选地，在泄出超临界二氧化碳或氮气之后，可以根据实际需要，再次通入超临界二氧化碳或氮气，加压并保持一段时间，从而进行二次浸润，这可以控制雏型品的发泡倍率。
实施例2：Elastollan 1180A发泡
将100重量份的Elastollan 1180A颗粒放至塑料射出机的进料桶中，然后经射出机螺杆给料熔融，并且经计量，射出至雏型模具内，从而成型为所需的雏型品，其中加工温度：130～200℃；雏型品尺寸：150mm×90mm×3～10mm。
接着，将此雏型品放置于温度为90～180℃的模具中。然后将二氧化碳在供应槽中调整至流体压力为6.9MPa～34.5MPa及温度为90～180℃，从而使槽内的二氧化碳处于超临界流体状态。
接着，打开模具上的超临界流体入口阀门，将超临界二氧化碳注入模具中，维持压力在6.9MPa～34.5MPa并保压10～50分钟。待超临 界流体浸润入雏型品后，向模具通入冷却液并泄出超临界流体，使雏型品发泡膨胀，打开模具即可得到具有所需结构和形状的发泡体成品。
实施例3：Elastollan 1185A发泡
将100重量份的Elastollan 1185A颗粒放至塑料射出机的进料桶中，然后经射出机螺杆给料熔融，并且经计量，射出至雏型模具内，从而成型为所需的雏型品，其中加工温度：130～200℃；尺寸：150mm×90mm×3～10mm。
接着，将此雏型品放置于温度为90～180℃的模具中。然后将二氧化碳在供应槽中调整至流体压力为6.9MPa～34.5MPa及温度为90～180℃，从而使槽内的二氧化碳处于超临界流体状态。
接着，打开模具上的超临界流体入口阀门，将超临界二氧化碳注入模具中，维持压力在6.9MPa～34.5MPa并保压10～50分钟。待超临界流体浸润入雏型品后，向模具通入冷却液并泄出超临界流体，使雏型品发泡膨胀，打开模具即可得到具有所需结构和形状的发泡体成品。
实施例4：Elastollan 1190A发泡
将100重量份的Elastollan 1190A颗粒放至塑料射出机的进料桶中，然后经射出机螺杆给料熔融，并且经计量，射出至雏型模具内，从而成型为所需之雏型品，其中加工温度：130～200℃；尺寸：150mm×90mm×3～10mm。
接着，将此雏型品放置于温度为90～180℃的模具中。然后将二氧化碳在供应槽中调整至流体压力为6.9MPa～34.5MPa及温度为90～180℃，从而使槽内的二氧化碳处于超临界流体状态。
接着，打开模具上的超临界流体入口阀门，将超临界二氧化碳注入模具中，维持压力在6.9MPa～34.5MPa并保压10～50分钟。待超临界流体浸润入雏型品后，向模具通入冷却液并泄出超临界流体，使雏型品发泡膨胀，打开模具即可得到具有所需结构和形状的发泡体成品。
实施例5：Elastollan 1180A及Elastollan 1185A之混合物发泡
将Elastollan 1180A颗粒及Elastollan 1185A颗粒放至塑料射出机的进料桶中，然后经射出机螺杆给料熔融，并且经计量，射出至雏型模具内，从而成型成所需的双硬度雏型品，其中加工温度：130～200℃；尺寸：150mm×90mm×3～10mm。
接着，将此双硬度雏型品放置于温度为90～150℃的模具中。然后将二氧化碳在供应槽中调整至流体压力为6.9MPa～34.5MPa及温度为90～150℃，从而使槽内的二氧化碳处于超临界流体状态。
接着，打开模具上的超临界流体入口阀门，将超临界二氧化碳注入模具中，维持压力在6.9MPa～34.5MPa并保压10～50分钟。待超临界流体浸润入雏型品后，向模具通入冷却液并泄出超临界流体，使雏型品发泡膨胀，打开模具即可得到具有所需结构和形状的发泡体成品。
实施例6-12
按照以下表1所示的材料及参数，采用与实施例1相同的工艺，制备具有所需结构和形状的发泡体成品。
表1
Figure PCTCN2016108378-appb-000003
以下参照表2，对上述实施例2至8的发泡体进行物性测试。测试的方式分别为ASTM D-2632(反弹性测试)、ASTM D-297(比重测试)、ASTM D-2240(硬度测试)。表2中所列的数据为至少三次重复试验的平均值。
表2
实施例 比重 平均孔径(微米) 平均回弹性(％) 发泡倍率 肖氏硬度
2 0.26 55 55 1.55 35
3 0.17 45 54 1.65 42
4 0.25 35 53 1.65 52
5 0.27 50 55/53 1.6 38/45
6 0.55 45 50 1.5 55
7 0.6 55 50 1.45 68
8 0.65 50 51 1.4 65
对于根据本公开的上述实施例所获得的发泡结构体成品，用手挤压成品表面，在变形达到10-20％时，开始出现不同程度的褶皱，当变形达到50％时，维持压缩3秒后松手，则褶皱立即消失。
此外，本公开的所有实施方案中，发泡结构体的主成份为热塑性高分子弹性体材料，发泡剂为超临界流体。此外，本公开的发泡体具有高回弹性、轻质量、无化学残留、环保、可100％回收，并且可以具有双硬度及高的发泡一致性。本公开的发泡结构体制造方法具有可量产、免二次加工、无毒环保与低制作成本等优点。
应理解应仅以描述性意义而不是为了限制的目的考虑本文所述的示例性实施方案。在各个示例性实施方案内的特征或方面的描述应通常被认为可用于其他示例性实施方案中的其他类似的特征或方面。
虽然在本文中已经描述了某些示例性实施方案和实施，但是其他实施方案和修改从该描述中会变得显而易见。因此，本发明的范围不限于此类实施方案，而限于所提出的权利要求限定的范围以及构成其技术特征的各种等同置换构成的范围。

Claims (12)

  1. 无褶皱发泡结构体，具有以ASTM D-2632方法测得的大于45％的平均回弹性系数并且具有小于等于99μm的平均孔径。
  2. 根据权利要求1所述的无褶皱发泡结构体，其中所述发泡结构体具有以ASTM D-2632方法测得的大于等于50％的平均回弹性系数，并且具有35μm至55μm的平均孔径。
  3. 根据权利要求1或2所述的无褶皱发泡结构体，其中所述发泡体结构具有以ASTM D-297方法测得的0.1至0.7的比重。
  4. 根据权利要求1至3中任一项所述的无褶皱发泡结构体，其中所述发泡体结构具有以ASTM D-297方法测得的0.17至0.65的比重。
  5. 根据权利要求1至4中任一项所述的无褶皱发泡结构体，其中所述发泡结构体具有单硬度或双硬度，并且所述硬度以通过ASTM D-2240方法测试的肖氏硬度计，各自为10至80。
  6. 根据权利要求1至5中任一项所述的无褶皱发泡结构体，其中所述硬度以通过ASTM D-2240方法测试的肖氏硬度计，各自为35至68。
  7. 根据权利要求1至6中任一项所述的无褶皱发泡结构体，其中所述发泡结构体的发泡倍率为1.4至1.7。
  8. 根据权利要求1至7中任一项所述的无褶皱发泡结构体，其中所述发泡结构体在被压缩或扭转变形时，当变形量达到10-20％即产生不同程度的褶皱，当形变达到50％时，外力维持10秒钟后释放，褶皱在0-600秒内消失。
  9. 根据权利要求1至8中任一项所述的无褶皱发泡结构体，其中所述发泡结构体在被压缩或扭转变形时，在变形量达到10-20％时即产生不同程度的褶皱，当变形达到50％时，外力维持3秒后释放，则褶皱在1秒内消失。
  10. 根据权利要求1至9中任一项所述的无褶皱发泡结构体，其中所述发泡结构体由一种或多种热塑性材料经超临界流体发泡制得，所述热塑性材料选自聚氨酯、橡胶、乙烯-乙酸乙烯酯、聚烯烃、聚苯乙烯共聚物、聚氯乙烯、聚对苯二甲酸乙二醇酯、热塑性丙烯酸酯及其任意组合，所述超临界流体选自二氧化碳、水、甲烷、乙烷、乙烯、丙烯、甲醇、乙醇、丙酮、氮气及其组合。
  11. 根据权利要求1至10中任一项所述的无褶皱发泡结构体，其中所述超临界流体选自二氧化碳、氮气及其组合，并且所述热塑性材料由以下式1表示的热塑性聚氨酯材料：
    Figure PCTCN2016108378-appb-100001
    其中，R1、R2各自独立地选自取代或未取代的直链或支链C1-12烷基、取代或未取代的苯基、取代或未取代的直链或支链C1-12烷基苯基、取代或未取代的直链或支链C1-12醚基、取代或未取代的直链或支链C1-12烷羟基、取代或未取代的直链或支链C1-12烷氧基或者取代或未取代的直链或支链C3-12环烷氧基，其中n为小于等于150的任意整数。
  12. 权利要求1至11中任一项所述的无褶皱发泡结构体在运动器材、包装材料以及鞋材中的用途。
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