WO2014142590A1 - Modificateur d'acide polylactique, procédé de préparation d'un modificateur d'acide polylactique, procédé pour modifier l'acide lactique l'employant, composition de mousse biodégradable employant le modificateur d'acide polylactique et mousse pour chaussures employant la composition de mousse biodégradable - Google Patents

Modificateur d'acide polylactique, procédé de préparation d'un modificateur d'acide polylactique, procédé pour modifier l'acide lactique l'employant, composition de mousse biodégradable employant le modificateur d'acide polylactique et mousse pour chaussures employant la composition de mousse biodégradable Download PDF

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WO2014142590A1
WO2014142590A1 PCT/KR2014/002138 KR2014002138W WO2014142590A1 WO 2014142590 A1 WO2014142590 A1 WO 2014142590A1 KR 2014002138 W KR2014002138 W KR 2014002138W WO 2014142590 A1 WO2014142590 A1 WO 2014142590A1
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polylactic acid
bis
tertbutylperoxy
formula
modified
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PCT/KR2014/002138
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English (en)
Korean (ko)
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최면천
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Choi Myeoncheon
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Priority claimed from KR1020130026591A external-priority patent/KR101563397B1/ko
Priority claimed from KR1020130050990A external-priority patent/KR101455528B1/ko
Application filed by Choi Myeoncheon filed Critical Choi Myeoncheon
Publication of WO2014142590A1 publication Critical patent/WO2014142590A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • 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
    • C08J9/06—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 chemical blowing agent
    • C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • 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
    • C08J9/06—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 chemical blowing agent
    • C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/107—Nitroso compounds
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/026—Crosslinking before of after foaming
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C08K5/1539—Cyclic anhydrides

Definitions

  • the present invention relates to a modifier of polylactic acid, and more particularly, to a polylactic acid modifier to modify polylactic acid and to use it as a biodegradable foam, a method for preparing a polylactic acid modifier, a polylactic acid modifier using the same, and a modified A biodegradable foam composition using polylactic acid and a shoe foam using the biodegradable foam composition.
  • Polylactic acid (PLA, poly (lactic acid), polylactic acid) is a biodegradable thermoplastic polyester with great potential to replace traditional petrochemical polymers. Possible polymer material.
  • Polylactic acid has the property of rapidly degrading and reproducing carbon dioxide under certain composting conditions, thus providing a more disposal option for these resins than most other organic polymers.
  • polylactic acid exhibits superior thermal processing properties in comparison to biopolymers such as polyethylene glycol and polycaprolactone in addition to the eco-friendliness, biocompatibility, and resource savings of biopolymers. Therefore, the use has been expanded to general consumption materials such as surgical sutures and prosthetics utilizing biocompatibility and bioabsorbability of polylactic acid, as well as packaging materials utilizing biodegradability, processability and transparency.
  • These packaging sectors include various rigid or semi-rigid articles such as 'clamshell' containers, prepared foods and other food serving trays and bottles or other containers.
  • Polylactic acid material has problems such as cracking point, slow decomposition rate, and hydrophobic point.
  • polylactic acid has high tensile strength, elastic modulus, and low elongation, and thus has poor impact resistance, thereby making it an obstacle to application to various packaging materials and elastic materials.
  • the slow biodegradation characteristics have a problem in the application to various general consumer goods as well as medical materials. Therefore, various attempts have been made to improve the impact resistance as well as the decomposition rate.
  • an object of the present invention is to improve the flexibility and biodegradability and can be used under various conditions, polylactic acid modifier, polylactic acid modifier manufacturing method, polylactic acid modified method using the same, modified polylactic acid
  • the present invention provides a biodegradable foam composition and a shoe foam using the biodegradable foam composition.
  • the modifier of polylactic acid according to the present invention is characterized in that it is composed of a compound of the following formula (1) in modifying polylactic acid using a modifier to polylactic acid (Poly Lactic Acid).
  • R 1 and R 2 are composed of one of the following Chemical Formulas 2 to 7)
  • R 3 is hydrogen or methyl group
  • R 4 is hydrogen or alkyl group of C 1 to C 8
  • n is 1 to 20
  • R 5 is hydrogen or an alkyl group of C 1 to C 8 , n is 1 to 20)
  • R 6 is hydrogen or an alkyl group of C 1 to C 8 , l + m + n is 3 to 20)
  • R 7 and R 8 are hydrogen or an alkyl group having 1 to C 8 , and l + m + n is 3 to 20.
  • R 9 and R 10 are hydrogen or a methyl group
  • R 11 is hydrogen or an alkyl group of C 1 to C 8
  • m + n is 2 to 20
  • R 12 and R 13 are hydrogen or a methyl group
  • R 14 is hydrogen or an alkyl group having 1 to 8 , 1 + m is 2 to 20, n is 1 to 5)
  • any one of polyethylene glycol monool, polyethylene glycol diol, polyethylene glycol triol and male anhydride is formed by the esterification reaction.
  • the method for modifying polylactic acid according to the present invention is a method for modifying polylactic acid, wherein the polylactic acid is modified using the above-described modifier.
  • polylactic acid reforming method according to the present invention is characterized by further adding an initiator during the polymerization to react.
  • the initiator 2,2 azobis (2,4-dimethylvaleronitrile), 2,2- azobisisobutyronitrile, 2,2- azodi (2-methylbutylonitrile), 1, 1-azobis (cyanacyclohexane), dimethyl-2,2-azobis (2-methylpropionate), 1-((cyano-1-methylethyl) azo) formamide, 2,5- Bis (tertbutylperoxy) -2,5-dimethyl-3-hexene, ditertbutyl peroxide, 2,5-bis (tertbutylperoxy) -2,5-dimethyl-hexene, dibenzoylperoxide, bis (Tertbutylperoxyisopropyl) benzene, butyl 4,4-bis (tertbutylperoxy) valerate, 1,1-bis (tertbutylperoxy) 3,3,5-trimethylchlorohexane, tertbutylperoxy It is characterized by being
  • the biodegradable foam composition according to the present invention is characterized by comprising the above-described modified polylactic acid and a mixed base and constituted by their foam polymerization.
  • the mixed base material is characterized by consisting of at least one of ethylene vinyl acetate copolymer, styrene isoprene styrene copolymer or ethylene methacrylate copolymer.
  • the polymerization is characterized in that it further comprises a cross-linking initiator and a blowing agent.
  • the crosslinking initiator is 2,5-bis (tertbutylperoxy) -2,5-dimethyl-3-hexene, ditertbutyl peroxide, 2,5-bis (tertbutylperoxy) -2,5-dimethyl -Hexene, dibenzoyl peroxide, bis (tertbutylperoxyisopropyl) benzene, butyl 4,4-bis (tertbutylperoxy) valerate, 1,1-bis (tertbutylperoxy) 3,3,5 Trimethylchlorohexane, tertbutylperoxybenzoate, lauryl peroxide and dicumyl peroxide.
  • the blowing agent is characterized by comprising at least one of an azodicarbonamide-based blowing agent or a dinitrosopentamethylenetetraamine-based blowing agent.
  • the shoe foam according to the present invention is characterized by comprising the biodegradable foam composition described above.
  • Another embodiment of the method for modifying polylactic acid according to the present invention is characterized by polymerizing polylactic acid (Poly Lactic Acid) into a molecule having a double bond and modifying it.
  • Poly Lactic Acid Poly Lactic Acid
  • the polymerization reaction is characterized in that the reaction is carried out dry.
  • the polylactic acid reforming method according to the present invention is characterized by further adding an initiator during the polymerization and reacting it.
  • the initiator is 2,2 azobis (2,4-dimethylvaleronitrile), 2,2-azobisisotropyronitrile, 2,2-azodi (2-methylbutylonitrile), 1,1- Azobis (cyanacyclohexane), dimethyl-2,2- azobis (2-methylpropionate), 1-((cyano-1-methylethyl) azo) formamide, 2,5-bis ( Tertbutylperoxy) -2,5-dimethyl-3-hexene, ditertbutyl peroxide, 2,5-bis (tertbutylperoxy) -2,5-dimethyl-hexene, dibenzoylperoxide, bis (tert Butyl peroxy isopropyl) benzene, butyl 4, 4-bis (tertbutyl peroxy) valerate, 1, 1-bis (tertbutyl peroxy) 3, 3, 5- trimethylchlorohexane, tert butyl peroxy benzoate , Lauryl peroxide, di
  • biodegradable foam composition according to the present invention is characterized by comprising the above-mentioned modified polylactic acid and a mixed base and constituted by their foam polymerization.
  • the mixed base material is characterized by consisting of at least one of ethylene vinyl acetate copolymer, styrene isoprene styrene copolymer or ethylene methacrylate copolymer.
  • the polymerization is characterized in that it further comprises a cross-linking initiator and a blowing agent.
  • the crosslinking agent is 2,5-bis (tertbutylperoxy) -2,5-dimethyl-3-hexene, ditertbutyl peroxide, 2,5-bis (tertbutylperoxy) -2,5-dimethyl- Hexene, dibenzoyl peroxide, bis (tertbutylperoxyisopropyl) benzene, butyl 4,4-bis (tertbutylperoxy) valerate, 1,1-bis (tertbutylperoxy) 3,3,5- Trimethylchlorohexane, tertbutylperoxybenzoate, lauryl peroxide, dicumyl peroxide, characterized in that it is composed of one or more.
  • the blowing agent is characterized by comprising at least one of an azodicarbonamide-based blowing agent or a dinitrosopentamethylenetetraamine-based blowing agent.
  • the foam for shoes according to the present invention is characterized by including the biodegradable foam composition described above.
  • a polylactic acid modifier a polylactic acid modifier production method, a polylactic acid modification method using the same, a biodegradable foam composition using the modified polylactic acid, and a shoe foam using the biodegradable foam composition have the following effects.
  • Figure 2 shows the mechanism by which a preferred embodiment of the modifier of polylactic acid according to the present invention is synthesized.
  • Figure 3 is a view showing the modification of the polylactic acid according to the present invention
  • FIG. 4 is a view showing a nuclear magnetic resonance spectrometer measurement results of a composition in which polyethylene glycol acrylate is blended with polylactic acid according to the present invention ((a) pure polylactic acid of Comparative Example 2, (b) modified polylactic acid of Example 20 )
  • Figure 4 is a view showing the infrared spectroscopy (FT-IR) measurement results of the composition blended polyethylene glycol acrylate to the polylactic acid according to the present invention ((a) pure polylactic acid of Comparative Example 2, (b) of Comparative Example 3 Simple blend, (c) modified polylactic acid of Example 20)
  • FT-IR infrared spectroscopy
  • FIG. 6 is a view showing a solvent extraction result of a composition in which polyethylene glycol acrylate is blended with polylactic acid according to the present invention ((a) pure polylactic acid of Comparative Example 2, (b) modified polylactic acid of Example 19, (c ) Simple blend of Comparative Example 4, (d) modified polylactic acid of Example 20, (e) simple blend of Comparative Example 3)
  • FIG. 7 is a view showing the differential scanning calorimetry (DSC Thermogram) measurement results of a composition in which polyethylene glycol acrylate is blended with polylactic acid according to the present invention ((a) pure polylactic acid of Comparative Example 2, (b) Example 19 Modified polylactic acid, (c) modified polylactic acid of Example 20, (d) modified polylactic acid of Example 21, (e) modified polylactic acid of Example 22)
  • DSC Thermogram differential scanning calorimetry
  • FIG. 8 is a view showing the results of measurement of biodegradability of a composition blended polyethylene glycol acrylate to polylactic acid according to the present invention ((a) pure polylactic acid of Comparative Example 2, (b) modified polylactic acid of Example 19, ( c) modified polylactic acid of Example 20, (d) modified polylactic acid of Example 21, (e) modified polylactic acid of Example 22)
  • FIG. 9 is a view showing a molecule of another embodiment for modifying the polylactic acid according to the present invention.
  • the constitution of the polylactic acid reforming method according to the present invention is characterized in that the polylactic acid (Poly Lactic Acid) is modified using polyethylene glycol maleate (Poly Ethylene Glycol Maleate).
  • polylactic acid is a polyester synthesized by polycondensation of lactic acid or ring-opening polymerization of lactide, and the intermediate of polyamide and polyethylene terephthalate (PET). It has physical properties and is mainly composed of natural vegetable sugar components obtained from potatoes and corn, which have high biodegradability but generally have high hardness, low elasticity, and poor durability.
  • the polymer can be synthesized in the form of poly-L-lactic acid, poly-D-lactic acid and poly-DL-lactic acid, depending on the steric structure of the monomer used in the synthesis.
  • poly-L-lactic acid (PLLA) synthesized using pure L-lactic acid or L-lactide is called crystalline polylactic acid because of its crystallinity, and mixed with D-lactic acid or D-lactide
  • PDLA amorphous polylactic acid
  • the initiator thermally decomposes to form a radical, and the radical forms hydrogen of the carbon to which the methyl group of the polylactic acid is bonded. It is taken away to form radicals on the polylactic acid chain.
  • a radical polymerization reaction by polyethylene glycol maleate occurs in the radical on the polylactic acid to produce a modified polylactic acid in which branched chains formed by monomers are formed on the polylactic acid chain.
  • the polylactic acid is due to the branches of the polyethylene glycol maleate, as shown in Figure 1, the tensile strength is lowered, the elastic modulus is lowered, the elongation is increased.
  • the polyethylene glycol maleate may be any material as long as it has a maleate group and can cause grafting coplolymerization to the polylactic acid.
  • any material may be applied as long as the material has the following formula (1).
  • R 1 and R 2 are composed of one of the following Chemical Formulas 2 to 7)
  • R 3 is hydrogen or methyl group
  • R 4 is hydrogen or alkyl group of C 1 to C 8
  • n is 1 to 20
  • R 5 is hydrogen or an alkyl group of C 1 to C 8 , n is 1 to 20)
  • R 6 is hydrogen or an alkyl group of C 1 to C 8 , l + m + n is 3 to 20)
  • R 7 and R 8 are hydrogen or an alkyl group having 1 to C 8 , and l + m + n is 3 to 20.
  • R 9 and R 10 are hydrogen or a methyl group
  • R 11 is hydrogen or an alkyl group of C 1 to C 8
  • m + n is 2 to 20
  • R 12 and R 13 are hydrogen or a methyl group
  • R 14 is hydrogen or an alkyl group having 1 to 8 , 1 + m is 2 to 20, n is 1 to 5)
  • an initiator may be further added and reacted during the polymerization.
  • the mechanism for synthesizing polyethylene glycol maleate, the modifier of the present invention is as shown in FIG. Any one of polyethylene glycol monool, polyethylene glycol diol, and polyethylene glycol triol may be mixed with maleic anhydride and then heated to esterify to produce a modifier of Chemical Formula 1, which is the modifier of the present invention.
  • a 500 ml sand dune flask is equipped with a stirrer, thermometer, inert gas, suction tube and condenser for condensation reaction.
  • 98 g of maleic anhydride and 124 g of ethylene glycol are added to the flask, followed by stirring while passing nitrogen gas at a flow rate of 100 ml / min.
  • the amount of water produced for the condensation reaction at 160 ° C. was obtained about 36 ml, and the temperature was maintained until the reaction was completed.
  • MEGMA Ethylene glycol maleate
  • a 500 ml sand dune flask is equipped with a stirrer, thermometer, inert gas, suction tube and condenser for condensation reaction.
  • 49 g of maleic anhydride and 150 g of triethylene glycol were added to the flask, and the mixture was stirred while passing nitrogen gas at a flow rate of 100 ml / min, and gradually heated. After slowly raising the temperature to 160 ° C. over about 1 hour, the amount of water produced for the condensation reaction at 160 ° C. was obtained about 36 ml, and the temperature was maintained until the reaction was completed.
  • Triethylene glycol maleate (TEGMA) was obtained after completion of the reaction.
  • a 500 ml sand dune flask is equipped with a stirrer, thermometer, inert gas, suction tube and condenser for condensation reaction.
  • 24.5 g of maleic anhydride and 200 g of polyethylene glycol (molecular weight 400) were added to the flask, and the mixture was stirred while passing nitrogen gas at a flow rate of 100 ml / min, and gradually heated. After slowly raising the temperature to 160 ° C. over about 1 hour, the amount of water produced for the condensation reaction at 160 ° C. was obtained about 36 ml, and the temperature was maintained until the reaction was completed. After the reaction was completed, polyethylene glycol maleate (PEG400MA) was obtained.
  • PEG400MA polyethylene glycol maleate
  • a 500 ml sand dune flask is equipped with a stirrer, thermometer, inert gas, suction tube and condenser for condensation reaction.
  • 12.25 g of maleic anhydride and 250 g of polyethylene glycol (molecular weight 1000) are added to the flask, and the mixture is stirred while passing nitrogen gas at a flow rate of 100 ml / min and gradually heating. After slowly raising the temperature to 160 ° C. over about 1 hour, the amount of water produced for the condensation reaction at 160 ° C. was obtained about 36 ml, and the temperature was maintained until the reaction was completed. After the reaction was completed, polyethylene glycol maleate (PEG1000MA) was obtained.
  • PEG1000MA polyethylene glycol maleate
  • a 500 ml sand dune flask is equipped with a stirrer, thermometer, inert gas, suction tube and condenser for condensation reaction.
  • 49 g of maleic anhydride and 192 g of tripropylene glycol were added to the flask, followed by stirring while passing nitrogen gas at a flow rate of 100 ml / min.
  • the amount of water produced for the condensation reaction at 160 ° C. was obtained about 36 ml, and the temperature was maintained until the reaction was completed.
  • Tripropylene glycol maleate (TPGMA) was obtained after completion
  • a 500 ml sand dune flask is equipped with a stirrer, thermometer, inert gas, suction tube and condenser for condensation reaction.
  • 24.5 g of maleic anhydride and 200 g of polyethylene glycol monomethyl ether (molecular weight 400) are added to the flask, and the mixture is heated while stirring while flowing nitrogen gas at a flow rate of 100 ml / min.
  • the amount of water produced for the condensation reaction at 160 ° C. was obtained about 36 ml, and the temperature was maintained until the reaction was completed.
  • Polyethylene glycol monomethyl ether maleate (MPEG400MA) was obtained after completion
  • PLA polylactic acid
  • a kneader which is a compound kneader
  • EGMA ethylene glycol maleate
  • DCP dicumyl peroxide
  • PLA polylactic acid
  • a kneader which is a compound kneader
  • TEGMA triethylene glycol maleate
  • DCP dicumyl peroxide
  • PVA polylactic acid
  • PEG400MA polyethylene glycol maleate
  • DCP dicumyl peroxide
  • PVA polylactic acid
  • PEG1000MA polyethylene glycol maleate
  • DCP dicumyl peroxide
  • PLA polylactic acid
  • TPGMA tripropylene glycol maleate
  • DCP dicumylperoxide
  • PLA polylactic acid
  • MPEG400MA polyethylene glycol monomethyl ether maleate
  • DCP dicumylperoxide
  • the biodegradable foam compositions may comprise polylactic acid (PLA), modified polylactic acid (PLEA), mixed substrates, crosslinking initiators and blowing agents.
  • the modified polylactic acid may be modified crystalline polylactic acid (PLLEA) or modified amorphous polylactic acid (PDLEA).
  • PLEA modified crystalline polylactic acid
  • PLEA modified amorphous polylactic acid
  • the mixed base may be an ethylene vinyl acetate copolymer (EVA, Ethylene-Vinyl Acetate copolymer), styrene isoprene styrene copolymer (SIS, Styrene-Isoprene Styrene copolymer) or ethylene methacrylate copolymer (EMA, Ethylene-Methacrylate copolymer) It may be used, which is a resin that is widely used as a foam because of excellent compressive strain, impact absorption, mechanical strength and the like.
  • EVA Ethylene-Vinyl Acetate copolymer
  • SIS Styrene-Isoprene Styrene copolymer
  • EMA Ethylene-Methacrylate copolymer
  • the crosslinking initiator may be an organic peroxide crosslinking initiator.
  • organic peroxide crosslinking initiator for example, 2,5-bis (tertbutyl peroxy) -2,5-dimethyl-3-hexene, ditertbutyl peroxide, 2,5-bis (tertbutyl peroxy) -2,5-dimethyl- Hexene, dibenzoyl peroxide, bis (tertbutylperoxyisopropyl) benzene, butyl 4,4-bis (tertbutylperoxy) valerate, 1,1-bis (tertbutylperoxy) 3,3,5- Trimethylchlorohexane, tertbutyl peroxybenzoate, lauryl peroxide, dicumyl peroxide can be used.
  • the blowing agent may be used alone or in combination with an azodicarbonamide blowing agent or a dinitrosopentamethylenetetraamine blowing agent.
  • an azodicarbonamide blowing agent or a dinitrosopentamethylenetetraamine blowing agent.
  • Kumyang Chemical's JTR series may be used.
  • Example 14 Example 15
  • Example 16 Example 17
  • Example 18 Comparative Example 1 PLA 1) 30 PL-EGMA 2) 30 PL-TEGMA 3) 30 PL-PEG400MA 4) 30 PL-PEG1000MA 5) 30 PL-TPGMA 6) 30 PL-MPEG400MA 7) 30 EVA 8) 70 70 70 70 70 DCP 9) 0.7 0.7 0.7 0.7 0.7 0.7 JTR 10) 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3
  • Comparative Example 1 30 parts by weight of polylactic acid (PLA) and 70 parts by weight of ethylene vinyl acetate (EVA) were kneaded at 180 degrees for 5 minutes using a compound kneader, kneader, to prepare a compound. Then, in a roll mill, 0.7 parts by weight of crosslinking initiator and 3.3 parts by weight of blowing agent are added to 100 parts by weight of the compound, and then uniformly mixed to prepare a 4 mm sheet-like compound. Thereafter, the sheet-like compound was introduced into a mold and then molded for about 20 minutes under a press condition of 170 degrees and 150 kg / cm 2 to prepare a foam.
  • PVA polylactic acid
  • EVA ethylene vinyl acetate
  • Example 13 kneaded at 180 degrees for 5 minutes using a compound kneader kneader compound 30 parts by weight of polylactic acid (PL-EGMA) modified by Example 7 and 70 parts by weight of ethylene vinyl acetate (EVA) compound was prepared. Then, in a roll mill, 0.7 parts by weight of crosslinking initiator and 3.3 parts by weight of blowing agent are added to 100 parts by weight of the compound, and then uniformly mixed to prepare a 4 mm sheet-like compound. Thereafter, the sheet-like compound was introduced into a mold and then molded for about 20 minutes under a press condition of 170 degrees and 150 kg / cm 2 to prepare a foam.
  • PL-EGMA polylactic acid
  • EVA ethylene vinyl acetate
  • Example 14 kneaded at 180 degrees for 5 minutes using a compound kneader kneader compound 30 parts by weight of polylactic acid (PL-TEGMA) modified by Example 8, 70 parts by weight of ethylene vinyl acetate (EVA) compound was prepared. Then, in a roll mill, 0.7 parts by weight of crosslinking initiator and 3.3 parts by weight of blowing agent are added to 100 parts by weight of the compound, and then uniformly mixed to prepare a 4 mm sheet-like compound. Thereafter, the sheet-like compound was introduced into a mold and then molded for about 20 minutes under a press condition of 170 degrees and 150 kg / cm 2 to prepare a foam.
  • PL-TEGMA polylactic acid
  • EVA ethylene vinyl acetate
  • Example 15 kneaded at 180 degrees for 5 minutes using a compound kneader compound kneader 30 parts by weight of polylactic acid (PL-PEG400MA), 70 parts by weight of ethylene vinyl acetate (EVA) modified by Example 9 was prepared. Then, in a roll mill, 0.7 parts by weight of crosslinking initiator and 3.3 parts by weight of blowing agent are added to 100 parts by weight of the compound, and then uniformly mixed to prepare a 4 mm sheet-like compound. Thereafter, the sheet-like compound was introduced into a mold and then molded for about 20 minutes under a press condition of 170 degrees and 150 kg / cm 2 to prepare a foam.
  • PL-PEG400MA polylactic acid
  • EVA ethylene vinyl acetate
  • Example 16 kneaded at 180 degrees for 5 minutes using a compound kneader kneader compound 30 parts by weight of polylactic acid (PL-PEG1000MA) modified by Example 10, 70 parts by weight of ethylene vinyl acetate (EVA) compound was prepared. Then, in a roll mill, 0.7 parts by weight of crosslinking initiator and 3.3 parts by weight of blowing agent are added to 100 parts by weight of the compound, and then uniformly mixed to prepare a 4 mm sheet-like compound. Thereafter, the sheet-like compound was introduced into a mold and then molded for about 20 minutes under a press condition of 170 degrees and 150 kg / cm 2 to prepare a foam.
  • PL-PEG1000MA polylactic acid
  • EVA ethylene vinyl acetate
  • Example 17 was kneaded at 180 degrees for 5 minutes using a compound kneader compound kneader 30 parts by weight of polylactic acid (PL-TPGMA) modified by Example 11, 70 parts by weight of ethylene vinyl acetate (EVA) compound was prepared. Then, in a roll mill, 0.7 parts by weight of crosslinking initiator and 3.3 parts by weight of blowing agent are added to 100 parts by weight of the compound, and then uniformly mixed to prepare a 4 mm sheet-like compound. Thereafter, the sheet-like compound was introduced into a mold and then molded for about 20 minutes under a press condition of 170 degrees and 150 kg / cm 2 to prepare a foam.
  • PL-TPGMA polylactic acid
  • EVA ethylene vinyl acetate
  • Example 18 kneaded at 180 degrees for 5 minutes using a compound kneader compound kneader 30 parts by weight of polylactic acid (PL-MPEG400MA), 70 parts by weight of ethylene vinyl acetate (EVA) modified by Example 11 compound was prepared. Then, in a roll mill, 0.7 parts by weight of crosslinking initiator and 3.3 parts by weight of blowing agent are added to 100 parts by weight of the compound, and then uniformly mixed to prepare a 4 mm sheet-like compound. Thereafter, the sheet-like compound was introduced into a mold and then molded for about 20 minutes under a press condition of 170 degrees and 150 kg / cm 2 to prepare a foam.
  • PL-MPEG400MA polylactic acid
  • EVA ethylene vinyl acetate
  • Example 14 Example 15
  • Example 16 Example 17
  • Example 18 Comparative Example 1 importance (g / cm -3 ) 0.21 0.22 0.22 0.23 0.22 0.22 0.21
  • the tensile strength (kg / cm 2 ) 25 26 27 30 25 26 18
  • Elongation % 415 420 427 390
  • 410 420
  • Tear strength (kg / cm) 14.7 15.3 15.6 15.7 14.9 15.2 9.3 Hardness Type D 52
  • 56 61 51 54
  • Examples 13 to 18 have a higher tensile strength, a higher elongation, and a larger elastic force. That is, the modified polylactic acid (PL-EGMA, PL-TEGMA, PL-PEG400MA, PL-PEG1000MA, PL-TPGMA, PL-MPEG400MA) shows soft physical properties, so it can be used as a foam material because of its excellent durability and flexibility. It can be seen that it is modified.
  • a plasticizer may be further added during the preparation of the biodegradable foam composition.
  • the plasticizer is a hydroxycarboxylic acid ester-based plasticizer, which may be used alone in tributyl o-acetylcitrate, triethyl oacetylcitrate, and tributyl citrate. Or in combination.
  • the constitution of the polylactic acid reforming method according to another embodiment of the present invention is to modify the polylactic acid by polymerizing it with a molecule having a double bond.
  • polylactic acid is a polyester synthesized by polycondensation of lactic acid or ring-opening polymerization of lactide, and the intermediate of polyamide and polyethylene terephthalate (PET). It has physical properties and is mainly composed of natural vegetable sugar components obtained from potatoes and corn, which have high biodegradability but generally have high hardness, low elasticity, and poor durability.
  • the polymer can be synthesized in the form of poly-L-lactic acid, poly-D-lactic acid and poly-DL-lactic acid, depending on the steric structure of the monomer used in the synthesis.
  • poly-L-lactic acid (PLLA) synthesized using pure L-lactic acid or L-lactide is called crystalline polylactic acid because of its crystallinity, and mixed with D-lactic acid or D-lactide
  • PDLA amorphous polylactic acid
  • the initiator is pyrolyzed to form a radical, and the radical is formed of a carbon to which a methyl group of the polylactic acid is bonded.
  • the hydrogen is taken away to form radicals on the polylactic acid chain.
  • a radical polymerization reaction by a monomer having a double bond in the radical on the polylactic acid may occur to produce a modified polylactic acid in which branched chains formed by monomers are formed on the polylactic acid chain.
  • the polymerization reaction is carried out dry because no other solvent is used during the reaction.
  • the polylactic acids Due to the branches of the double bond molecule, the polylactic acids have a lower tensile strength, a lower elastic modulus, and a higher elongation as shown in FIG. 6.
  • the molecules having the double bond may be applied to any material that can cause grafting coplolymerization to the polylactic acid.
  • an initiator may be further added and reacted during the polymerization.
  • Example 21 Example 22
  • Example 23 PLLA 1) 100 80 90 90 80 70 60 PDLA 2) 80 PEGA 3) 20 10 10 20 30 40 20 DCP 4) 0.8 0.8 0.8 0.8 0.8 0.8 0.8
  • Comparative Example 2 was prepared by 0.1 to 2mm sheet by hot pressing at 180 °C 100 parts by weight of pure crystalline polylactic acid (PLLA, Natureworks, 4032D) using a hot press.
  • PLLA pure crystalline polylactic acid
  • Comparative Example 3 80 parts by weight of crystalline polylactic acid (PLLA) was melted and heated at 180 ° C. in a kneader compound kneader, and then 20 parts by weight of polyethylene glycol acrylate (PEGA) was added and kneaded for 5 minutes to prepare a simple blending compound. Prepared. The compound thus prepared was thermally compressed at 180 ° C. using a hot press to prepare a sheet of 0.1 to 2 mm.
  • PLLA crystalline polylactic acid
  • PEGA polyethylene glycol acrylate
  • Comparative Example 4 90 parts by weight of crystalline polylactic acid (PLLA) was melted by heating to 180 in a compound kneader kneader, and then 10 parts by weight of polyethylene glycol acrylate (PEGA) was added and kneaded for 5 minutes to prepare a simple blending compound. It was. The compound thus prepared was thermally compressed at 180 using a hot press to prepare a sheet of 0.1 to 2 mm.
  • PLLA crystalline polylactic acid
  • PEGA polyethylene glycol acrylate
  • Example 19 90 parts by weight of crystalline polylactic acid (PLLA) was heated and melted at 180 ° C. in a kneader, which is a compound kneader, and 10 parts by weight of polyethylene glycol acrylate (PEGA) was added and kneaded for 5 minutes. Thereafter, 0.8 parts by weight of dicumylperoxide (DCP), which is an initiator, was further added, followed by reactive blending at 180 ° C. for 10 minutes to prepare modified polylactic acid. The compound thus prepared was thermally compressed at 180 ° C. using a hot press to prepare a sheet of 0.1 to 2 mm.
  • PLLA crystalline polylactic acid
  • PEGA polyethylene glycol acrylate
  • DCP dicumylperoxide
  • Example 20 80 parts by weight of crystalline polylactic acid (PLLA) was melted by heating at 180 ° C. in a kneader, which is a compound kneader, and then kneaded for 5 minutes after adding 20 parts by weight of polyethylene glycol acrylate (PEGA). Thereafter, 0.8 parts by weight of dicumylperoxide (DCP), which is an initiator, was further added, followed by reactive blending at 180 ° C. for 10 minutes to prepare modified polylactic acid. The compound thus prepared was thermally compressed at 180 ° C. using a hot press to prepare a sheet of 0.1 to 2 mm.
  • DCP dicumylperoxide
  • Example 21 70 parts by weight of crystalline polylactic acid (PLLA) was melted by heating at 180 ° C. in a kneader, which is a compound kneader, and then kneaded for 5 minutes after 30 parts by weight of polyethylene glycol acrylate (PEGA) was added. Thereafter, 0.8 parts by weight of dicumylperoxide (DCP), which is an initiator, was further added, followed by reactive blending at 180 ° C. for 10 minutes to prepare modified polylactic acid. The compound thus prepared was thermally compressed at 180 ° C. using a hot press to prepare a sheet of 0.1 to 2 mm.
  • PLLA crystalline polylactic acid
  • PEGA polyethylene glycol acrylate
  • DCP dicumylperoxide
  • the compound thus prepared was thermally compressed at 180 ° C. using a hot press to prepare a sheet of 0.1 to 2 mm.
  • Example 22 60 parts by weight of crystalline polylactic acid (PLLA) was melted by heating at 180 ° C. in a kneader, which is a compound kneader, and then 40 parts by weight of polyethylene glycol acrylate (PEGA) was kneaded for 5 minutes. Thereafter, 0.8 parts by weight of dicumylperoxide (DCP), which is an initiator, was further added, followed by reactive blending at 180 ° C. for 10 minutes to prepare modified polylactic acid. The compound thus prepared was thermally compressed at 180 ° C. using a hot press to prepare a sheet of 0.1 to 2 mm.
  • PLLA crystalline polylactic acid
  • PEGA polyethylene glycol acrylate
  • DCP dicumylperoxide
  • Example 23 80 parts by weight of amorphous polylactic acid (PDLA) was melted by heating to 180 in a compound kneader kneader, and then 40 parts by weight of polyethylene glycol acrylate (PEGA) was kneaded for 5 minutes. Thereafter, 0.8 parts by weight of dicumylperoxide (DCP), which is an initiator, was further added, followed by reactive blending for 180 minutes to prepare modified polylactic acid. The compound thus prepared was thermally compressed at 180 using a hot press to prepare a sheet of 0.1 to 2 mm.
  • PDLA amorphous polylactic acid
  • PEGA polyethylene glycol acrylate
  • DCP dicumylperoxide
  • Comparative Examples 2 to 4 and Examples 19 to 23 as described above were subjected to structural analysis, solvent extraction, thermomechanical analysis, tensile property analysis, and biodegradation property analysis, respectively.
  • PLA polylactic acid
  • PEGA polyethylene glycol acrylate
  • NMR nuclear magnetic resonance spectroscopy
  • FTIR Fourier transform infrared spectroscopy
  • Solvent extraction is carried out using polylactic acid (SLA) using soxhlet method using polylactic acid (PLA), modified polylactic acid (PLEA) and polylactic acid (PLA) / polyethylene glycol acrylate (PEGA) simple blend. The amount of acrylate unbound in PLA) was confirmed.
  • Example 19 modified by a reactive blend of polylactic acid (PLA) and polyethylene glycol acrylate (PEGA) (Comparative Example 4, comparison) Compared with Example 3), the modification was effectively performed because the amount of the solvent dissolved and extracted by the solvent was very small.
  • PLA polylactic acid
  • PEGA polyethylene glycol acrylate
  • DSC differential scanning calorimetry
  • the glass transition temperature is falling as more polyethylene glycol acrylate (PEGA) is added, and in the case of modified polylactic acid (PLEA) as compared to pure polylactic acid (PLA), the glass transition phenomenon is clear. It is not clearly distinguished and appears in a wide range. This result shows that the acrylate grafted to polylactic acid (PLA) weakens the rigidity of the polylactic acid (PLA) chain so that the modified polylactic acid has soft physical properties at room temperature.
  • PEGA polyethylene glycol acrylate
  • PDA modified polylactic acid
  • PLA polylactic acid
  • Tensile properties were analyzed by using a universal testing machine (UTM) to measure the tensile strength, modulus and elongation of the modified polylactic acid.
  • UPM universal testing machine
  • Example 19 Example 20
  • Example 21 Example 22
  • Example 23 The tensile strength MPa 51 49 37 28 14 35 Modulus of elasticity MPa 1290 1070 880 690 440 760 Elongation % 4.6 6.1 9.5 10.8 17.8 11.3
  • the modified polylactic acid shows a small tensile strength and elastic modulus, and it can be seen that the elongation is increased, and this tendency increases as the amount of added polyethylene glycol acrylate is increased. It can be seen that the increase. From this result, it can be seen that the modified polylactic acid shows soft and flexible physical properties compared to pure polylactic acid.
  • Biodegradation characterization was performed by measuring modified polylactic acid (PLEA) having a thickness of 0.1 mm and a size of 2 * 2 cm in a NaHCO 3 / NaOH buffer solution having a pH of 10.7 to measure the degradation rate in the aqueous base solution.
  • PPA modified polylactic acid
  • the biodegradable foam compositions may comprise polylactic acid (PLA), modified polylactic acid (PLEA), mixed substrates, crosslinking initiators and blowing agents.
  • the modified polylactic acid may be modified crystalline polylactic acid (PLLEA) or modified amorphous polylactic acid (PDLEA).
  • PLEA modified crystalline polylactic acid
  • PLEA modified amorphous polylactic acid
  • the mixed base may be an ethylene vinyl acetate copolymer (EVA, Ethylene-Vinyl Acetate copolymer), styrene isoprene styrene copolymer (SIS, Styrene-Isoprene Styrene copolymer) or ethylene methacrylate copolymer (EMA, Ethylene-Methacrylate copolymer) It may be used, which is a resin that is widely used as a foam because of excellent compressive strain, impact absorption, mechanical strength and the like.
  • EVA Ethylene-Vinyl Acetate copolymer
  • SIS Styrene-Isoprene Styrene copolymer
  • EMA Ethylene-Methacrylate copolymer
  • the crosslinking initiator may be an organic peroxide crosslinking initiator.
  • organic peroxide crosslinking initiator for example, 2,5-bis (tertbutyl peroxy) -2,5-dimethyl-3-hexene, ditertbutyl peroxide, 2,5-bis (tertbutyl peroxy) -2,5-dimethyl- Hexene, dibenzoyl peroxide, bis (tertbutylperoxyisopropyl) benzene, butyl 4,4-bis (tertbutylperoxy) valerate, 1,1-bis (tertbutylperoxy) 3,3,5- Trimethylchlorohexane, tertbutyl peroxybenzoate, lauryl peroxide, dicumyl peroxide can be used.
  • the blowing agent may be used alone or in combination with an azodicarbonamide blowing agent or a dinitrosopentamethylenetetraamine blowing agent.
  • an azodicarbonamide blowing agent or a dinitrosopentamethylenetetraamine blowing agent.
  • Kumyang Chemical's JTR series may be used.
  • Example 29 PLLA 1) 30 PLLEA20 2) 10 20 30 50 70 PDLEA20 3) 30 EVA 4) 70 90 80 70 50 30 70 Crosslinking initiator 5) 0.7 0.7 0.7 0.7 0.7 Blowing agent 6) 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5
  • Comparative Example 5 30 parts by weight of crystalline polylactic acid (PLLA) and 70 parts by weight of ethylene vinyl acetate (EVA) were kneaded at 180 degrees for 5 minutes using a compound kneader, kneader, to prepare a compound. Then, in a roll mill, 0.7 parts by weight of crosslinking initiator and 4.5 parts by weight of blowing agent are added to 100 parts by weight of the compound, and then uniformly mixed to prepare a 4 mm sheet-like compound. Thereafter, the sheet-like compound was introduced into a mold and then molded for about 20 minutes under a press condition of 170 degrees and 150 kg / cm 2 to prepare a foam.
  • PLLA crystalline polylactic acid
  • EVA ethylene vinyl acetate
  • Example 24 10 parts by weight of modified crystalline polylactic acid (PLLEA20) and 90 parts by weight of ethylene vinyl acetate (EVA) were kneaded at 180 degrees for 5 minutes using a compound kneader, kneader, to prepare a compound. Then, in a roll mill, 0.7 parts by weight of crosslinking initiator and 4.5 parts by weight of blowing agent are added to 100 parts by weight of the compound, and then uniformly mixed to prepare a 4 mm sheet-like compound. Thereafter, the sheet-like compound was introduced into a mold and then molded for about 20 minutes under a press condition of 170 degrees and 150 kg / cm 2 to prepare a foam.
  • PLEA20 modified crystalline polylactic acid
  • EVA ethylene vinyl acetate
  • Example 25 20 parts by weight of modified crystalline polylactic acid (PLLEA20) and 80 parts by weight of ethylene vinyl acetate (EVA) were kneaded at 180 degrees for 5 minutes using a compound kneader, kneader, to prepare a compound. Then, in a roll mill, 0.7 parts by weight of crosslinking initiator and 4.5 parts by weight of blowing agent are added to 100 parts by weight of the compound, and then uniformly mixed to prepare a 4 mm sheet-like compound. Thereafter, the sheet-like compound was introduced into a mold and then molded for about 20 minutes under a press condition of 170 degrees and 150 kg / cm 2 to prepare a foam.
  • PLEA20 modified crystalline polylactic acid
  • EVA ethylene vinyl acetate
  • Example 26 30 parts by weight of modified crystalline polylactic acid (PLLEA20) and 70 parts by weight of ethylene vinyl acetate (EVA) were kneaded at 180 degrees for 5 minutes using a compound kneader, kneader, to prepare a compound. Then, in a roll mill, 0.7 parts by weight of crosslinking initiator and 4.5 parts by weight of blowing agent are added to 100 parts by weight of the compound, and then uniformly mixed to prepare a 4 mm sheet-like compound. Thereafter, the sheet-like compound was introduced into a mold and then molded for about 20 minutes under a press condition of 170 degrees and 150 kg / cm 2 to prepare a foam.
  • PLEA20 modified crystalline polylactic acid
  • EVA ethylene vinyl acetate
  • Example 27 50 parts by weight of modified crystalline polylactic acid (PLLEA20) and 50 parts by weight of ethylene vinyl acetate (EVA) were kneaded at 180 degrees for 5 minutes using a compound kneader, kneader, to prepare a compound. Then, in a roll mill, 0.7 parts by weight of crosslinking initiator and 4.5 parts by weight of blowing agent are added to 100 parts by weight of the compound, and then uniformly mixed to prepare a 4 mm sheet-like compound. Thereafter, the sheet-like compound was introduced into a mold and then molded for about 20 minutes under a press condition of 170 degrees and 150 kg / cm 2 to prepare a foam.
  • PLEA20 modified crystalline polylactic acid
  • EVA ethylene vinyl acetate
  • Example 28 70 parts by weight of modified crystalline polylactic acid (PLLEA20) and 30 parts by weight of ethylene vinyl acetate (EVA) were kneaded at 180 degrees for 5 minutes using a compound kneader, kneader, to prepare a compound. Then, in a roll mill, 0.7 parts by weight of crosslinking initiator and 4.5 parts by weight of blowing agent are added to 100 parts by weight of the compound, and then uniformly mixed to prepare a 4 mm sheet-like compound. Thereafter, the sheet-like compound was introduced into a mold and then molded for about 20 minutes under a press condition of 170 degrees and 150 kg / cm 2 to prepare a foam.
  • PLEA20 modified crystalline polylactic acid
  • EVA ethylene vinyl acetate
  • Example 29 30 parts by weight of modified amorphous polylactic acid (PDLEA20) and 70 parts by weight of ethylene vinyl acetate (EVA) were kneaded at 180 degrees for 5 minutes using a compound kneader, kneader, to prepare a compound. Then, in a roll mill, 0.7 parts by weight of crosslinking initiator and 4.5 parts by weight of blowing agent are added to 100 parts by weight of the compound, and then uniformly mixed to prepare a 4 mm sheet-like compound. Thereafter, the sheet-like compound was introduced into a mold and then molded for about 20 minutes under a press condition of 170 degrees and 150 kg / cm 2 to prepare a foam.
  • PLEA20 modified amorphous polylactic acid
  • EVA ethylene vinyl acetate
  • Examples 24 to 29 can be seen that the tensile strength is high, the elongation is increased, the elastic force is also large. That is, since the modified polylactic acid shows soft physical properties, it can be seen that it is modified to be used as a foam material because of its excellent durability and flexibility.
  • Example 31 Example 32 PLVA20 1) 30 PLEM20 2) 30 PLVU2 03) 30 EVA 4) 70 70 70 Crosslinking initiator 5) 0.7 0.7 0.7 Blowing agent 6) 4.5 4.5 4.5 4.5
  • it may comprise a modified polylactic acid (PLVA, PLEM, PLAU), mixed base, crosslinking initiator and blowing agent.
  • PLVA polylactic acid
  • PLEM PLEM
  • PLAU polylactic acid
  • composition of the polylactic acid reforming method according to the present invention is modified by polymerizing polylactic acid (Poly Lactic Acid) with vinyl acetate, polyvinyl glycol maleate or allyl polyurethane. It is.
  • the polylactic acid was prepared in the same manner as in Example 20 except that vinyl acetate, polyethylene glycol maleate or allyl polyurethane was used instead of the polyethylene glycol acrylate used in Example 2.
  • Example 30 parts by weight of crystalline polylactic acid (PLVA20) modified with vinyl acetate and 70 parts by weight of ethylene vinyl acetate (EVA) were kneaded at 180 degrees using a kneader, which is a compound kneader, to prepare a compound. .
  • a kneader which is a compound kneader
  • blowing agent 0.7 parts by weight of crosslinking initiator and 4.5 parts by weight of blowing agent are added to 100 parts by weight of the compound, and then uniformly mixed to prepare a 4 mm sheet-like compound. Thereafter, the sheet-like compound was introduced into a mold and then molded for about 20 minutes under a press condition of 170 degrees and 150 kg / cm 2 to prepare a foam.
  • Example 31 30 parts by weight of crystalline polylactic acid (PLEM20) modified with polyethylene glycol maleate and 70 parts by weight of ethylene vinyl acetate (EVA) were kneaded at 180 degrees using a kneader, which is a compound kneader, for 5 minutes. Prepared. Then, in a roll mill, 0.7 parts by weight of crosslinking initiator and 4.5 parts by weight of blowing agent are added to 100 parts by weight of the compound, and then uniformly mixed to prepare a 4 mm sheet-like compound. Thereafter, the sheet-like compound was introduced into a mold and then molded for about 20 minutes under a press condition of 170 degrees and 150 kg / cm 2 to prepare a foam.
  • PLM20 crystalline polylactic acid
  • EVA ethylene vinyl acetate
  • Example 32 30 parts by weight of crystalline polylactic acid (PLAU20) modified with allyl polyurethane and 70 parts by weight of ethylene vinyl acetate (EVA) were kneaded at 180 degrees for 5 minutes using a compound kneader, kneader, to prepare a compound. It was. Then, in a roll mill, 0.7 parts by weight of crosslinking initiator and 4.5 parts by weight of blowing agent are added to 100 parts by weight of the compound, and then uniformly mixed to prepare a 4 mm sheet-like compound. Thereafter, the sheet-like compound was introduced into a mold and then molded for about 20 minutes under a press condition of 170 degrees and 150 kg / cm 2 to prepare a foam.
  • PLAU20 crystalline polylactic acid
  • EVA ethylene vinyl acetate
  • Example 12 Example 13, and Example 14, which are different from each other, will be described in detail.
  • Example 32 importance g / cm 3 0.22 0.20 0.20 The tensile strength kg / cm 2 26 22 23 Elongation % 420 460 450 Tear strength kg / cm 15.3 13.2 13.6 Elasticity % 39 35 38
  • Examples 30 to 32 can be seen that the tensile strength is high, the elongation is increased, the elastic force is also large. That is, since the modified polylactic acid (PLVA20, PLEM20, PLAU20) shows a soft physical properties, it can be seen that it is modified to be used as a foam material with excellent durability and flexibility.
  • PLVA20, PLEM20, PLAU20 shows a soft physical properties, it can be seen that it is modified to be used as a foam material with excellent durability and flexibility.
  • a plasticizer may be further added during the preparation of the biodegradable foam composition.
  • the plasticizer is a hydroxycarboxylic acid ester-based plasticizer, which may be used alone in tributyl o-acetylcitrate, triethyl oacetylcitrate, and tributyl citrate. Or in combination.
  • a polylactic acid modifier in the present invention, a polylactic acid modifier, a polylactic acid modifier manufacturing method, a polylactic acid reforming method using the same, a biodegradable foam composition using a modified polylactic acid and a shoe foam using a biodegradable foam composition than the use of polylactic acid in tensile strength and It has low elastic modulus, high elongation, soft properties, excellent durability and flexibility, and excellent biodegradability, so it can be used as a foam material for biodegradable shoe midsole.

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Abstract

La présente invention concerne un procédé pour modifier un acide polylactique et une composition de mousse biodégradable l'employant. Le procédé pour modifier un acide polylactique se caractérise en ce que l'acide polylactique se polymérise pour être modifié en une molécule ayant une double liaison, et la composition de mousse biodégradable se caractérise en ce qu'elle est produite par mélange et polymérisation de l'acide polylactique modifié et d'une substance de mélange.
PCT/KR2014/002138 2013-03-13 2014-03-13 Modificateur d'acide polylactique, procédé de préparation d'un modificateur d'acide polylactique, procédé pour modifier l'acide lactique l'employant, composition de mousse biodégradable employant le modificateur d'acide polylactique et mousse pour chaussures employant la composition de mousse biodégradable WO2014142590A1 (fr)

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KR1020130026591A KR101563397B1 (ko) 2013-03-13 2013-03-13 폴리락트산의 개질방법, 개질된 폴리락트산을 이용한 생분해성 발포체 조성물 및 생분해성 발포체 조성물을 이용한 신발용 발포체
KR10-2013-0026591 2013-03-13
KR1020130050990A KR101455528B1 (ko) 2013-05-07 2013-05-07 폴리락트산의 개질제, 폴리락트산 개질제 제조방법, 이를 이용한 폴리락트산 개질방법, 개질된 폴리락트산을 이용한 생분해성 발포체 조성물 및 생분해성 발포체 조성물을 이용한 신발용 발포체
KR10-2013-0050990 2013-05-07

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CN112409551A (zh) * 2020-11-26 2021-02-26 四会市邦得利化工有限公司 一种可降解聚乳酸树脂成膜乳液及其制备方法及应用
CN113943405A (zh) * 2021-05-08 2022-01-18 天津科技大学 一种折痕自修复聚乳酸薄膜
CN114106310A (zh) * 2021-12-30 2022-03-01 华东理工大学 一种高结晶耐热聚乳酸材料及其制备方法
CN114685882A (zh) * 2022-04-03 2022-07-01 杭州师范大学 一种反应性微交联弹性体及其制备方法、应用

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