WO2014054846A1 - Method of producing vegetable-oil-based biomass elastomer and elastomer produced by the method - Google Patents

Method of producing vegetable-oil-based biomass elastomer and elastomer produced by the method Download PDF

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WO2014054846A1
WO2014054846A1 PCT/KR2013/003893 KR2013003893W WO2014054846A1 WO 2014054846 A1 WO2014054846 A1 WO 2014054846A1 KR 2013003893 W KR2013003893 W KR 2013003893W WO 2014054846 A1 WO2014054846 A1 WO 2014054846A1
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styrene
polymer
butadiene
oil
vegetable
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PCT/KR2013/003893
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French (fr)
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Jin Kuk Kim
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Industry-Academic Cooperation Foundation Gyeongsang National University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
    • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to a method of producing a vegetable-oil-based biomass elastomer and an elastomer produced by the method. More particularly, the present invention pertains to a method of producing a biomass elastomer by causing a polymer containing styrene and butadiene or a diene-based polymer having terminals reformed by functional groups to react with vegetable oil or an extract thereof.
  • An elastomer refers to a substance having elasticity that enables the substance to change its shape in response to an external force and to recover its original form upon the removal of the force.
  • One representative example of the elastomer is rubber.
  • the rubber includes natural rubber obtained from a rubber tree and synthetic rubber obtained by polymerizing isoprene.
  • the natural rubber is structurally the same as the natural rubber.
  • a biomass is a biological organic body including a plant growing with solar energy, a microorganism, a plant body created by photosynthesis, a fungus body and an animal body living on these bodies.
  • the biomass which is reproducible and environment-friendly, draws attention as an important resource that can substitute petroleum resources.
  • chemical substances such as a polymer and the like, it is a recent trend to, in light of the price and the environment protection, develop and produce a biomass-based plastic (biomass plastic) using a biomass as a raw material.
  • the biomass plastic is a very useful material from the viewpoint of carbon emission reduction because carbon dioxide existing in the air is consumed in the process of photosynthesis for generating a biomass as a raw material of the biomass plastic.
  • biomass plastic examples include a starch-based plastic produced through the use of starch and a polylactide (PLA) produced by transforming corn to glucose, lactic acid or lactide.
  • PHA polylactide
  • the starch-based plastic and the polylactide are biomass plastics exhibiting biodegradability.
  • polyester-based biomass plastic such as poly lactic acid or poly trimethylene terephthalate.
  • the polyester-based biomass plastic is formed into films or fibers and is mainly used in the field of general-purpose plastics.
  • a polyamide-based plastic using ricinoleic acid of castor oil as its raw material such as polyamide 11 (having a melting point of 187°C) or polyamide 610 (having a melting point of 215°C), is available in the field of engineering plastics requiring heat resistance.
  • Polyamide 4 having a melting point of 260°C
  • the biomass plastics set forth above still remain low in physical properties such as incombustibility, impact resistance, heat resistance and formability.
  • the biomass plastics are restrictively used in some products such as a food container or a packaging material.
  • the present inventors have repeatedly conducted experiments in an effort to find a method of producing a reusable biomass elastomer having improved physical properties and an elastomer produced by the method.
  • the present inventors have succeeded in producing a vegetable-oil-based recyclable biomass elastomer which is superior in workability, elasticity and critical performance.
  • Another object of the present invention is to provide a method of producing a biomass elastomer by causing a diene-based polymer having terminals reformed by functional groups to react with a vegetable oil extract and an elastomer produced by the method.
  • the present invention provides a method of producing a vegetable-oil-based biomass elastomer, including: a step of producing a polymer selected from the group consisting of a styrene-butadiene-styrene block copolymer, a styrene-butadiene block polymer and a styrene-butadiene random polymer; and a step of adding vegetable oil to the polymer and subjecting the polymer and the vegetable oil to coupling reaction.
  • the method may further include: a step of mixing zinc oxide (ZnO), stearic acid, an antioxidant, sulfur (S) and a vulcanizing accelerator with the biomass elastomer obtained after the coupling reaction and vulcanizing the biomass elastomer.
  • ZnO zinc oxide
  • S sulfur
  • a vulcanizing accelerator with the biomass elastomer obtained after the coupling reaction and vulcanizing the biomass elastomer.
  • the polymer and the vegetable oil in the step of adding vegetable oil, may be mixed in a molar ratio of 1:0.2 to 3.
  • the step of adding vegetable oil may be performed for 30 to 140 minutes at a temperature of 25 to 55°C.
  • the styrene-butadiene-styrene block copolymer may be produced by a method comprising the steps of: heating a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane to a temperature of 35 to 45°C; adding 30 to 70 wt% of styrene monomers on the basis of the total amount of the styrene monomers to be used to the heated solvent; adding an initiator to the solvent added with the styrene monomers and then adding butadiene monomers to the solvent; and adding the remaining 30 to 70 wt% of the styrene monomers to the solvent added with the butadiene monomers.
  • a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methyl
  • the styrene-butadiene block polymer may be produced by a method comprising the steps of: heating a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane to a temperature of 35 to 45°C; adding styrene monomers to the heated solvent; and adding an initiator to the solvent added with the styrene monomers and then adding butadiene monomers to the solvent.
  • a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane
  • the styrene-butadiene random polymer may be produced by a method comprising the steps of: adding styrene monomers and butadiene monomers to a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane and heating the solvent to a temperature of 35 to 45°C; and adding an initiator to the heated solvent.
  • a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane
  • the present invention provides a vegetable-oil-based biomass elastomer produced by the aforementioned method.
  • the present invention provides a method of producing a vegetable-oil-based biomass elastomer, including: a step (first step) of reforming terminals of a diene-based polymer with functional groups; a step (second step) of obtaining fatty acid by purifying vegetable oil; and a step (third step) of producing a biomass elastomer by subjecting the diene-based polymer, the terminals of which are reformed by the functional groups in the first step, to polymerization reaction with the fatty acid of the vegetable oil.
  • the present invention provides a method of producing a vegetable-oil-based biomass elastomer, including: a step (first step) of reforming terminals of a diene-based polymer with functional groups; and a step (second step) of producing a biomass elastomer by subjecting the diene-based polymer, the terminals of which are reformed by the functional groups in the first step, to polymerization reaction with fatty acid.
  • the diene-based polymer may be selected from the group consisting of styrene butadiene rubber, butadiene rubber and styrene butadiene styrene rubber.
  • the styrene butadiene rubber may contain styrene monomers and butadiene monomers in a weight ratio of 25:75.
  • the diene-based polymer may have a molecular weight of 10,000 to 100,000.
  • the functional groups may include amino groups, hydroxyl groups and carboxyl groups.
  • the terminals of the diene-based polymer may be reformed with amino groups through the use of 4-bromo-N,N-bis(trimethylsilyl)aniline.
  • the polymerization reaction of the diene-based polymer, the terminals of which are reformed by the functional groups in the first step, with the fatty acid may be performed at a temperature of 200 to 250°C.
  • the present invention provides a vegetable-oil-based biomass elastomer produced by the aforementioned method.
  • a vegetable-oil-based biomass elastomer is produced by a first method of subjecting a polymer containing styrene and butadiene to coupling reaction with vegetable oil, a second method of subjecting a diene-based polymer, the terminals of which are reformed by functional groups, to polymerization reaction with fatty acid obtained from purified vegetable oil, or a third method of subjecting a diene-based polymer, the terminals of which are reformed by functional groups, to polymerization reaction with fatty acid.
  • the vegetable-oil-based biomass elastomer produced by the present method can be widely used, as a hybrid material of petrochemical substance and natural substance capable of substituting a petroleum-derived polymer material, in different industrial fields such as a medical field, a footwear material field, a car component material field and an electric and electronic component material field.
  • Fig. 1 shows a GPC (Gel Permeation Chromatography) analysis result of a pure styrene-butadiene-styrene block copolymer.
  • Fig. 2 shows a GPC analysis result of one example of a vegetable-oil-based biomass elastomer produced by the present method (using a styrene-butadiene-styrene block copolymer).
  • Fig. 3 shows a 1 H-NMR (Nuclear Magnetic Resonance) analysis result of a pure styrene-butadiene-styrene block copolymer.
  • Fig. 4 shows a 1 H-NMR analysis result of one example of a vegetable-oil-based biomass elastomer produced by the present method (using a styrene-butadiene-styrene block copolymer).
  • Fig. 5 shows a GPC analysis result of a pure styrene-butadiene block polymer.
  • Fig. 6 shows a GPC analysis result of one example of a vegetable-oil-based biomass elastomer produced by the present method (using a styrene-butadiene block polymer).
  • Fig. 7 shows a 1 H-NMR analysis result of a pure styrene-butadiene block polymer.
  • Fig. 8 shows a 1 H-NMR analysis result of one example of a vegetable-oil-based biomass elastomer produced by the present method (using a styrene-butadiene block polymer).
  • Fig. 9 shows a GPC analysis result of a pure styrene-butadiene random polymer.
  • Fig. 10 shows a GPC analysis result of one example of a vegetable-oil-based biomass elastomer produced by the present method (using a styrene-butadiene random polymer).
  • Fig. 11 shows a 1 H-NMR analysis result of a pure styrene-butadiene random polymer.
  • Fig. 12 shows a 1 H-NMR analysis result of one example of a vegetable-oil-based biomass elastomer produced by the present method (using a styrene-butadiene random polymer).
  • Fig. 13 shows a 1 H-NMR analysis spectrum of waste vegetable oil.
  • Fig. 14 shows a FT-IR analysis spectrum of waste vegetable oil.
  • Fig. 15 shows a 1 H-NMR analysis spectrum of fatty acid obtained by filtering waste vegetable oil.
  • Fig. 16 shows a 1 H-NMR analysis spectrum of an environment-friendly elastomer according to one embodiment of the present invention.
  • a method of producing a vegetable-oil-based biomass elastomer including: a step (first step) of producing a polymer selected from the group consisting of a styrene-butadiene-styrene block copolymer, a styrene-butadiene block polymer and a styrene-butadiene random polymer; and a step (second step) of adding vegetable oil to the polymer and subjecting the polymer and the vegetable oil to coupling reaction.
  • the first step is a step of producing a polymer selected from the group consisting of a styrene-butadiene-styrene block copolymer, a styrene-butadiene block polymer and a styrene-butadiene random polymer.
  • the styrene-butadiene-styrene block copolymer can be produced by a method including the steps of: heating a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane to a temperature of 35 to 45°C; adding 30 to 70 wt% of styrene monomers on the basis of the total amount of the styrene monomers to be used to the heated solvent; adding an initiator to the solvent added with the styrene monomers and then adding butadiene monomers to the solvent; and adding the remaining 30 to 70 wt% of the styrene monomers to the solvent added with the butadiene monomers.
  • a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcycl
  • the styrene-butadiene block polymer can be produced by a method including the steps of: heating a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane to a temperature of 35 to 45°C; adding styrene monomers to the heated solvent; and adding an initiator to the solvent added with the styrene monomers and then adding butadiene monomers to the solvent.
  • a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane
  • the styrene-butadiene random polymer can be produced by a method including the steps of: adding styrene monomers and butadiene monomers to a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane and heating the solvent to a temperature of 35 to 45°C; and adding an initiator to the heated solvent.
  • a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane
  • the initiator may be an initiator typically used in the field of the present invention.
  • the initiator may be n-butyllithium.
  • the styrene and the butadiene are mixed in a weight ratio of 1:0.8 to 4, preferably in a weight ratio of 1:1 to 2.5.
  • the second step is a step of adding vegetable oil to the polymer and subjecting the polymer and the vegetable oil to coupling reaction.
  • the vegetable oil may be selected from the group consisting of canola oil, corn oil, cottolene, flaxseed oil, olive oil, rapeseed oil, soybean oil and sunflower oil but is not limited thereto. In the present method, it is also possible to use waste oil of the aforementioned vegetable oil.
  • the polymer produced in the first step and the vegetable oil are mixed in a molar ratio of 1:0.2 to 3, preferably in a molar ratio of 1:0.5 to 2, more preferably in a molar ratio of 1:0.7 to 1.2.
  • the coupling reaction step is preferably performed for 30 to 140 minutes at a temperature of 25 to 55°C, more preferably for 60 to 120 minutes at a temperature of 35 to 45°C, even more preferably for 80 to 100 minutes at a temperature of 38 to 40°C.
  • the molecular weight of the biomass elastomer produced by the present method is preferably 1.5 to 3 times as large as the molecular weight of the polymer.
  • the present method may further include a step (third step) of mixing zinc oxide (ZnO), stearic acid, an antioxidant, sulfur (S) and a vulcanizing accelerator with the biomass elastomer obtained after the coupling reaction and vulcanizing the biomass elastomer.
  • ZnO zinc oxide
  • S sulfur
  • a vulcanizing accelerator 1 to 10 weight parts of the zinc oxide, 0.5 to 5 weight parts of the stearic acid, 0.5 to 2.5 weight parts of the antioxidant, 0.5 to 5 weight parts of the sulfur and 0.5 to 5 weight parts of the vulcanizing accelerator are preferably mixed with 100 weight parts of the biomass elastomer.
  • the vulcanizing is performed preferably at a temperature of 140 to 220°C, more preferably at a temperature of 170 to 180°C.
  • the antioxidant may be an antioxidant typically used in the field of the present invention.
  • the antioxidant may be dibutyl hydroxyl toluene (BHT).
  • the vulcanizing accelerator may be a vulcanizing accelerator typically used in the field of the present invention.
  • the vulcanizing accelerator may be N-cyclohexyl-2-benzothiazoyl sulfonamide (CBS).
  • the biomass elastomer produced by the present method is higher in tensile strength, highly resistant to swelling and wear and capable of maintaining elasticity over a broad temperature range.
  • a method of producing a vegetable-oil-based environment-friendly biomass elastomer including: a step (first step) of reforming terminals of a diene-based polymer with functional groups; a step (second step) of obtaining fatty acid by purifying vegetable oil; and a step (third step) of producing a biomass elastomer by subjecting the diene-based polymer, the terminals of which are reformed by the functional groups in the first step, to polymerization reaction with the fatty acid of the vegetable oil.
  • the first step is a step of reforming terminals of a diene-based polymer with functional groups.
  • the diene-based polymer has different kinds of microstructures in terms of the molecular. structure. Different types of copolymers exist in the diene-based polymer. This makes it possible to produce elastomers having different physical properties.
  • examples of the diene-based polymer include styrene butadiene rubber (SBR), butadiene rubber (BR) and styrene butadiene styrene (SBS). It is preferable to use styrene butadiene rubber as the diene-based polymer.
  • SBR styrene butadiene rubber
  • BR butadiene rubber
  • SBS styrene butadiene styrene
  • the diene-based polymer can be produced by a polymerizing method ordinarily used in the art.
  • the styrene butadiene rubber can be polymerized to have a desired molecular weight by adding n-butyllithium catalyst to styrene monomers and butadiene monomers.
  • the present invention is not limited thereto.
  • the styrene butadiene rubber may contain styrene monomers and butadiene monomers in different weight ratios, preferably in a weight ratio of 25:75.
  • the diene-based polymer has a molecular weight of 10,000 or more, preferably a molecular weight of 10,000 to 100,000.
  • the styrene butadiene rubber having a molecular weight of 10,000 or more can be produced by putting styrene monomers and butadiene monomers into an autoclave in a weight ratio of 25:75, adding n-butyllithium as an initiator and polymerizing the styrene monomers and the butadiene monomers.
  • the terminals of the diene-based polymer can be reformed different kinds of functional groups.
  • the functional groups it is possible to use amino groups, hydroxyl groups, carboxyl groups and so forth.
  • the present invention is not limited thereto.
  • a method known in the art can be used in reforming the terminals of the diene-based polymer with the functional groups.
  • the terminals of the diene-based polymer can be reformed with amino groups through the use of 4-bromo-N,N-bis(trimethylsilyl)aniline.
  • the second step is a step of obtaining fatty acid by purifying waste vegetable oil.
  • the waste vegetable oil may be selected from the group consisting of soybean oil, sunflower oil and palm oil.
  • the present invention is not limited thereto.
  • the 1 H-NMR analysis and the FT-IR analysis reveal that the waste vegetable oil is composed of triglyceride.
  • the 1 H-NMR analysis reveals that the fatty acid obtained by filtering and purifying the waste vegetable oil is unsaturated hydrocarbon whose terminals are composed of carboxyl groups. Accordingly, the fatty acid can be easily coupled to the terminals of the diene-based polymer reformed by the functional groups.
  • the fatty acid can be obtained from waste vegetable oil.
  • the waste vegetable oil can be purified by a method ordinarily used in the art.
  • the present invention is not limited thereto.
  • the third step is a step of producing a biomass elastomer by subjecting the diene-based polymer, the terminals of which are reformed by the functional groups in the second step, to polymerization reaction with the fatty acid of the waste vegetable oil.
  • the polymerization reaction can be performed within an autoclave preferably at a reaction temperature of 200 to 250°C.
  • the vegetable-oil-based biomass elastomer according to the present invention is produced by using a biomass, one of recyclable organic resources, as a raw material, combining the biomass with diene-based polymer and reforming the terminals of the diene-based polymer with functional groups. This makes it possible to produce a natural-substance-based environment-friendly recyclable elastomer having superior critical performance.
  • the vegetable-oil-based biomass elastomer according to the present invention can be widely used in different industrial fields such as a medical field, a footwear material field, a car component material field and an electric and electronic component material field.
  • Production of a biomass elastomer was started at a temperature of 40°C by using cyclohexane as a solvent and using n-butyllithium as an initiator. 380 ml of cyclohexane was heated to 40°C. 25 ml of styrene monomers were added to the heated cyclohexane. Then, 3 ml of n-butyllithium and 70 g of butadiene monomers were added to the heated cyclohexane in the named order.
  • SBS styrene-butadiene-styrene
  • reaction process for producing the biomass elastomer of example 1 is as follows (reaction formulae 1 to 4).
  • Reaction Formula 1 Reaction of Styrene and n-Butyllithium
  • Reaction Formula 4 Formation of Styrene-Butadiene-Styrene/Waste-Vegetable-Oil-Based Biomass Elastomer
  • Fig. 1 shows a GPC analysis result of a pure SBS block copolymer.
  • Fig. 2 shows a GPC analysis result of the biomass elastomer produced in example 1 (the SBS/waste-vegetable-oil-based biomass elastomer).
  • the GPC analysis result shown in Fig. 1 is directed to a pure SBS block copolymer having a molecular weight of 25,000.
  • the GPC analysis result shown in Fig. 2 is directed to a SBS/waste-vegetable-oil-based biomass elastomer having a molecular weight of 50,000.
  • Fig. 3 shows a 1 H-NMR analysis result of a pure SBS block copolymer.
  • Fig. 4 shows a 1 H-NMR analysis result of the biomass elastomer produced in example 1 (the SBS/waste-vegetable-oil-based biomass elastomer).
  • Production of a biomass elastomer was started at a temperature of 40°C by using cyclohexane as a solvent and using n-butyllithium as an initiator. 380 ml of cyclohexane was heated to 40°C. 50 ml of styrene monomers were added to the heated cyclohexane. Then, 3 ml of n-butyllithium and 70 g of butadiene monomers were added to the heated cyclohexane in the named order, thereby producing a styrene-butadiene (SB) block polymer.
  • SB styrene-butadiene
  • reaction process for producing the biomass elastomer of example 2 is as follows (reaction formulae 1, 2 and 5).
  • Reaction Formula 1 Reaction of Styrene and n-Butyllithium
  • Reaction Formula 5 Formation of Styrene-Butadiene-Di-block-Polymer/Waste-Vegetable-Oil-Based Biomass Elastomer
  • Fig. 5 shows a GPC analysis result of a pure SB block polymer.
  • Fig. 6 shows a GPC analysis result of the biomass elastomer produced in example 2 (the SB-block-polymer/waste-vegetable-oil-based biomass elastomer).
  • the GPC analysis result shown in Fig. 5 is directed to a pure SB block polymer having a molecular weight of 25,000.
  • the GPC analysis result shown in Fig. 6 is directed to a SB-block-polymer/waste-vegetable-oil-based biomass elastomer having a molecular weight of 50,000.
  • Fig. 7 shows a 1 H-NMR spectrum of a pure SB block polymer.
  • Fig. 8 shows a 1 H-NMR analysis result of the biomass elastomer produced in example 2 (the SB-block-polymer/waste-vegetable-oil-based biomass elastomer).
  • Production of a biomass elastomer was started at a temperature of 40°C by using cyclohexane as a solvent and using n-butyllithium as an initiator. 50 ml of styrene monomers and 70 g of butadiene monomers were added to 380 ml of cyclohexane. The mixture was heated to 40°C. Then, 3 ml of n-butyllithium were added to the heated mixture, thereby producing a styrene-butadiene (SB) random polymer. 3 g of waste soybean oil was added to the SB random polymer thus produced, consequently subjecting the SB random polymer and the waste soybean oil to coupling reaction. 5 ml of methyl alcohol as a reaction terminator was added to stop the coupling reaction, thus producing a biomass elastomer.
  • SB styrene-butadiene
  • reaction process for producing the biomass elastomer of example 3 is as follows (reaction formulae 6 and 7).
  • Reaction Formula 7 Formation of Styrene-Butadiene-Random-Polymer/Waste-Vegetable-Oil-Based Biomass Elastomer
  • Fig. 9 shows a GPC analysis result of a pure SB random polymer.
  • Fig. 10 shows a GPC analysis result of the biomass elastomer produced in example 3 (the SB-random-polymer/waste-vegetable-oil-based biomass elastomer).
  • the GPC analysis result shown in Fig. 9 is directed to a pure SB random polymer having a molecular weight of 25,000.
  • the GPC analysis result shown in Fig. 10 is directed to a SB-random-polymer/waste-vegetable-oil-based biomass elastomer having a molecular weight of 50,000.
  • Fig. 11 shows a 1 H-NMR spectrum of a pure SB random polymer.
  • Fig. 12 shows a 1 H-NMR analysis result of the biomass elastomer produced in example 3 (the SB-random-polymer/waste-vegetable-oil-based biomass elastomer).
  • 100 g of the biomass elastomer produced in example 2 5.0 g of zinc oxide, 1.5 g of stearic acid, 1.0 g of BHT, 1.25 g of sulfur and 2.0 g of CBS were mixed and subjected to heat treatment at a temperature of 160 to 170°C, thereby producing a biomass elastomer.
  • 100 g of the biomass elastomer produced in example 3 5.0 g of zinc oxide, 1.5 g of stearic acid, 1.0 g of BHT, 1.25 g of sulfur and 2.0 g of CBS were mixed and subjected to heat treatment at a temperature of 160 to 170°C, thereby producing a biomass elastomer.
  • Styrene monomers, butadiene monomers and n-butyllithium as an initiator were put into an autoclave and are subjected to polymerization reaction. At this time, the styrene monomers and the butadiene monomers were added in a weight ratio of 25:75, thereby producing styrene-butadiene rubber.
  • Waste vegetable oil was treated with methanol to separate fatty acid and waste glycerol.
  • the waste glycerol was used to separate glycerol (95%) and fatty acid (5%).
  • the waste glycerol and water were filled into a beaker in a ratio of 4:1 and were stirred by a stirrer.
  • the pH of the mixture was adjusted by adding 35.0% of HCl little by little. While stirring the mixture, sampling was performed by a pH meter and the pH of the mixture measured by pH paper was adjusted to become equal to 3. After precipitation reaction, fatty acid was obtained from the waste vegetable oil.
  • the styrene-butadiene rubber obtained in the first step, the terminals of which are reformed with NH 2 , and the fatty acid obtained in the second step were put into an autoclave and were subjected to reaction for three hours at a temperature of 200 to 250°C, thereby producing a biomass elastomer.
  • FIG. 16 The 1 H-NMR spectrum of the environment-friendly biomass elastomer thus produced is shown in Fig. 16. It can be appreciated in Fig. 16 that the styrene-butadiene rubber and the fatty acid are well coupled to each other in the biomass elastomer.
  • the vegetable-oil-based biomass elastomer produced by the present method can be widely used, as a hybrid material of petrochemical substance and natural substance capable of substituting a petroleum-derived polymer material, in different industrial fields such as a medical field, a footwear material field, a car component material field and an electric and electronic component material field.

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Abstract

A method of producing a vegetable-oil-based biomass elastomer includes a step of producing a polymer selected from the group consisting of a styrene-butadiene-styrene block copolymer, a styrene-butadiene block polymer and a styrene-butadiene random polymer, and a step of adding vegetable oil to the polymer and subjecting the polymer and the vegetable oil to coupling reaction.

Description

METHOD OF PRODUCING VEGETABLE-OIL-BASED BIOMASS ELASTOMER AND ELASTOMER PRODUCED BY THE METHOD
The present invention relates to a method of producing a vegetable-oil-based biomass elastomer and an elastomer produced by the method. More particularly, the present invention pertains to a method of producing a biomass elastomer by causing a polymer containing styrene and butadiene or a diene-based polymer having terminals reformed by functional groups to react with vegetable oil or an extract thereof.
An elastomer refers to a substance having elasticity that enables the substance to change its shape in response to an external force and to recover its original form upon the removal of the force. One representative example of the elastomer is rubber. The rubber includes natural rubber obtained from a rubber tree and synthetic rubber obtained by polymerizing isoprene. The natural rubber is structurally the same as the natural rubber.
Along with the industrial development, rubber is extensively used in different fields of industry. In terms of supply-demand balance, physical properties and heat resistance, natural rubber as a naturally occurring material has limitations in using the same as component materials. In contrast, synthetic rubber as a petrochemical product meets with a problem of limited petroleum resources and generates a large amount of carbon dioxide, thereby posing a problem of global warming.
A biomass is a biological organic body including a plant growing with solar energy, a microorganism, a plant body created by photosynthesis, a fungus body and an animal body living on these bodies. The biomass, which is reproducible and environment-friendly, draws attention as an important resource that can substitute petroleum resources. In the industry of chemical substances such as a polymer and the like, it is a recent trend to, in light of the price and the environment protection, develop and produce a biomass-based plastic (biomass plastic) using a biomass as a raw material.
The biomass plastic is a very useful material from the viewpoint of carbon emission reduction because carbon dioxide existing in the air is consumed in the process of photosynthesis for generating a biomass as a raw material of the biomass plastic.
Representative examples of the biomass plastic include a starch-based plastic produced through the use of starch and a polylactide (PLA) produced by transforming corn to glucose, lactic acid or lactide. The starch-based plastic and the polylactide are biomass plastics exhibiting biodegradability.
As an example of the biomass plastics obtained by chemical synthesis, there is a polyester-based biomass plastic such as poly lactic acid or poly trimethylene terephthalate. The polyester-based biomass plastic is formed into films or fibers and is mainly used in the field of general-purpose plastics. On the other hand, a polyamide-based plastic using ricinoleic acid of castor oil as its raw material, such as polyamide 11 (having a melting point of 187℃) or polyamide 610 (having a melting point of 215℃), is available in the field of engineering plastics requiring heat resistance. Research and development on polyamide 4 (having a melting point of 260℃) is being made in order to practically use polyamide 4 in the high-added-value application requiring high physical properties.
As compared with conventional plastics using petroleum as its raw material, the biomass plastics set forth above still remain low in physical properties such as incombustibility, impact resistance, heat resistance and formability. At the present time, there is a problem in that the biomass plastics are restrictively used in some products such as a food container or a packaging material.
Under these circumstances, the present inventors have repeatedly conducted experiments in an effort to find a method of producing a reusable biomass elastomer having improved physical properties and an elastomer produced by the method. As a result of the experiments, the present inventors have succeeded in producing a vegetable-oil-based recyclable biomass elastomer which is superior in workability, elasticity and critical performance.
It is therefore an object of the present invention to provide a method of producing a vegetable-oil-based biomass elastomer and an elastomer produced by the method. More particularly, it is an object of the present invention to provide a method of producing a biomass elastomer using a polymer containing styrene and butadiene and vegetable oil and an elastomer produced by the method.
Another object of the present invention is to provide a method of producing a biomass elastomer by causing a diene-based polymer having terminals reformed by functional groups to react with a vegetable oil extract and an elastomer produced by the method.
In order to achieve the above objects, the present invention provides a method of producing a vegetable-oil-based biomass elastomer, including: a step of producing a polymer selected from the group consisting of a styrene-butadiene-styrene block copolymer, a styrene-butadiene block polymer and a styrene-butadiene random polymer; and a step of adding vegetable oil to the polymer and subjecting the polymer and the vegetable oil to coupling reaction.
In one embodiment of the present invention, the method may further include: a step of mixing zinc oxide (ZnO), stearic acid, an antioxidant, sulfur (S) and a vulcanizing accelerator with the biomass elastomer obtained after the coupling reaction and vulcanizing the biomass elastomer.
In one embodiment of the present invention, in the step of adding vegetable oil, the polymer and the vegetable oil may be mixed in a molar ratio of 1:0.2 to 3.
In one embodiment of the present invention, the step of adding vegetable oil may be performed for 30 to 140 minutes at a temperature of 25 to 55℃.
In one embodiment of the present invention, the styrene-butadiene-styrene block copolymer may be produced by a method comprising the steps of: heating a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane to a temperature of 35 to 45℃; adding 30 to 70 wt% of styrene monomers on the basis of the total amount of the styrene monomers to be used to the heated solvent; adding an initiator to the solvent added with the styrene monomers and then adding butadiene monomers to the solvent; and adding the remaining 30 to 70 wt% of the styrene monomers to the solvent added with the butadiene monomers.
In one embodiment of the present invention, the styrene-butadiene block polymer may be produced by a method comprising the steps of: heating a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane to a temperature of 35 to 45℃; adding styrene monomers to the heated solvent; and adding an initiator to the solvent added with the styrene monomers and then adding butadiene monomers to the solvent.
In one embodiment of the present invention, the styrene-butadiene random polymer may be produced by a method comprising the steps of: adding styrene monomers and butadiene monomers to a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane and heating the solvent to a temperature of 35 to 45℃; and adding an initiator to the heated solvent.
The present invention provides a vegetable-oil-based biomass elastomer produced by the aforementioned method.
The present invention provides a method of producing a vegetable-oil-based biomass elastomer, including: a step (first step) of reforming terminals of a diene-based polymer with functional groups; a step (second step) of obtaining fatty acid by purifying vegetable oil; and a step (third step) of producing a biomass elastomer by subjecting the diene-based polymer, the terminals of which are reformed by the functional groups in the first step, to polymerization reaction with the fatty acid of the vegetable oil.
The present invention provides a method of producing a vegetable-oil-based biomass elastomer, including: a step (first step) of reforming terminals of a diene-based polymer with functional groups; and a step (second step) of producing a biomass elastomer by subjecting the diene-based polymer, the terminals of which are reformed by the functional groups in the first step, to polymerization reaction with fatty acid.
In one embodiment of the present invention, the diene-based polymer may be selected from the group consisting of styrene butadiene rubber, butadiene rubber and styrene butadiene styrene rubber.
In one embodiment of the present invention, the styrene butadiene rubber may contain styrene monomers and butadiene monomers in a weight ratio of 25:75.
In one embodiment of the present invention, the diene-based polymer may have a molecular weight of 10,000 to 100,000.
In one embodiment of the present invention, the functional groups may include amino groups, hydroxyl groups and carboxyl groups.
In one embodiment of the present invention, in the first step, the terminals of the diene-based polymer may be reformed with amino groups through the use of 4-bromo-N,N-bis(trimethylsilyl)aniline.
In one embodiment of the present invention, the polymerization reaction of the diene-based polymer, the terminals of which are reformed by the functional groups in the first step, with the fatty acid may be performed at a temperature of 200 to 250℃.
The present invention provides a vegetable-oil-based biomass elastomer produced by the aforementioned method.
According to the present invention, a vegetable-oil-based biomass elastomer is produced by a first method of subjecting a polymer containing styrene and butadiene to coupling reaction with vegetable oil, a second method of subjecting a diene-based polymer, the terminals of which are reformed by functional groups, to polymerization reaction with fatty acid obtained from purified vegetable oil, or a third method of subjecting a diene-based polymer, the terminals of which are reformed by functional groups, to polymerization reaction with fatty acid. This makes it possible to provide a recyclable biomass elastomer which is superior in workability, elasticity and critical performance. Accordingly, the vegetable-oil-based biomass elastomer produced by the present method can be widely used, as a hybrid material of petrochemical substance and natural substance capable of substituting a petroleum-derived polymer material, in different industrial fields such as a medical field, a footwear material field, a car component material field and an electric and electronic component material field.
Fig. 1 shows a GPC (Gel Permeation Chromatography) analysis result of a pure styrene-butadiene-styrene block copolymer.
Fig. 2 shows a GPC analysis result of one example of a vegetable-oil-based biomass elastomer produced by the present method (using a styrene-butadiene-styrene block copolymer).
Fig. 3 shows a 1H-NMR (Nuclear Magnetic Resonance) analysis result of a pure styrene-butadiene-styrene block copolymer.
Fig. 4 shows a 1H-NMR analysis result of one example of a vegetable-oil-based biomass elastomer produced by the present method (using a styrene-butadiene-styrene block copolymer).
Fig. 5 shows a GPC analysis result of a pure styrene-butadiene block polymer.
Fig. 6 shows a GPC analysis result of one example of a vegetable-oil-based biomass elastomer produced by the present method (using a styrene-butadiene block polymer).
Fig. 7 shows a 1H-NMR analysis result of a pure styrene-butadiene block polymer.
Fig. 8 shows a 1H-NMR analysis result of one example of a vegetable-oil-based biomass elastomer produced by the present method (using a styrene-butadiene block polymer).
Fig. 9 shows a GPC analysis result of a pure styrene-butadiene random polymer.
Fig. 10 shows a GPC analysis result of one example of a vegetable-oil-based biomass elastomer produced by the present method (using a styrene-butadiene random polymer).
Fig. 11 shows a 1H-NMR analysis result of a pure styrene-butadiene random polymer.
Fig. 12 shows a 1H-NMR analysis result of one example of a vegetable-oil-based biomass elastomer produced by the present method (using a styrene-butadiene random polymer).
Fig. 13 shows a 1H-NMR analysis spectrum of waste vegetable oil.
Fig. 14 shows a FT-IR analysis spectrum of waste vegetable oil.
Fig. 15 shows a 1H-NMR analysis spectrum of fatty acid obtained by filtering waste vegetable oil.
Fig. 16 shows a 1H-NMR analysis spectrum of an environment-friendly elastomer according to one embodiment of the present invention.
Certain preferred embodiment of the present invention will now be described in detail with reference to the accompanying drawings.
According to the present invention, there is provided a method of producing a vegetable-oil-based biomass elastomer, including: a step (first step) of producing a polymer selected from the group consisting of a styrene-butadiene-styrene block copolymer, a styrene-butadiene block polymer and a styrene-butadiene random polymer; and a step (second step) of adding vegetable oil to the polymer and subjecting the polymer and the vegetable oil to coupling reaction.
The first step is a step of producing a polymer selected from the group consisting of a styrene-butadiene-styrene block copolymer, a styrene-butadiene block polymer and a styrene-butadiene random polymer.
In the first step of the present method, the styrene-butadiene-styrene block copolymer can be produced by a method including the steps of: heating a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane to a temperature of 35 to 45℃; adding 30 to 70 wt% of styrene monomers on the basis of the total amount of the styrene monomers to be used to the heated solvent; adding an initiator to the solvent added with the styrene monomers and then adding butadiene monomers to the solvent; and adding the remaining 30 to 70 wt% of the styrene monomers to the solvent added with the butadiene monomers.
In the first step of the present method, the styrene-butadiene block polymer can be produced by a method including the steps of: heating a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane to a temperature of 35 to 45℃; adding styrene monomers to the heated solvent; and adding an initiator to the solvent added with the styrene monomers and then adding butadiene monomers to the solvent.
In the first step of the present method, the styrene-butadiene random polymer can be produced by a method including the steps of: adding styrene monomers and butadiene monomers to a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane and heating the solvent to a temperature of 35 to 45℃; and adding an initiator to the heated solvent.
In the polymer producing step (first step) of the present method, the initiator may be an initiator typically used in the field of the present invention. Preferably, the initiator may be n-butyllithium.
In the first step of the present method, the styrene and the butadiene are mixed in a weight ratio of 1:0.8 to 4, preferably in a weight ratio of 1:1 to 2.5.
The second step is a step of adding vegetable oil to the polymer and subjecting the polymer and the vegetable oil to coupling reaction.
In the present method, the vegetable oil may be selected from the group consisting of canola oil, corn oil, cottolene, flaxseed oil, olive oil, rapeseed oil, soybean oil and sunflower oil but is not limited thereto. In the present method, it is also possible to use waste oil of the aforementioned vegetable oil.
In the coupling reaction step (second step) of the present method, the polymer produced in the first step and the vegetable oil are mixed in a molar ratio of 1:0.2 to 3, preferably in a molar ratio of 1:0.5 to 2, more preferably in a molar ratio of 1:0.7 to 1.2.
In the present method, the coupling reaction step is preferably performed for 30 to 140 minutes at a temperature of 25 to 55℃, more preferably for 60 to 120 minutes at a temperature of 35 to 45℃, even more preferably for 80 to 100 minutes at a temperature of 38 to 40℃.
The molecular weight of the biomass elastomer produced by the present method is preferably 1.5 to 3 times as large as the molecular weight of the polymer.
The present method may further include a step (third step) of mixing zinc oxide (ZnO), stearic acid, an antioxidant, sulfur (S) and a vulcanizing accelerator with the biomass elastomer obtained after the coupling reaction and vulcanizing the biomass elastomer. At this time, 1 to 10 weight parts of the zinc oxide, 0.5 to 5 weight parts of the stearic acid, 0.5 to 2.5 weight parts of the antioxidant, 0.5 to 5 weight parts of the sulfur and 0.5 to 5 weight parts of the vulcanizing accelerator are preferably mixed with 100 weight parts of the biomass elastomer.
In the present method, the vulcanizing is performed preferably at a temperature of 140 to 220℃, more preferably at a temperature of 170 to 180℃.
In the present method, the antioxidant may be an antioxidant typically used in the field of the present invention. Preferably, the antioxidant may be dibutyl hydroxyl toluene (BHT).
In the present method, the vulcanizing accelerator may be a vulcanizing accelerator typically used in the field of the present invention. Preferably, the vulcanizing accelerator may be N-cyclohexyl-2-benzothiazoyl sulfonamide (CBS).
When vulcanized, the biomass elastomer produced by the present method is higher in tensile strength, highly resistant to swelling and wear and capable of maintaining elasticity over a broad temperature range.
According to the present invention, there is also provided a method of producing a vegetable-oil-based environment-friendly biomass elastomer, including: a step (first step) of reforming terminals of a diene-based polymer with functional groups; a step (second step) of obtaining fatty acid by purifying vegetable oil; and a step (third step) of producing a biomass elastomer by subjecting the diene-based polymer, the terminals of which are reformed by the functional groups in the first step, to polymerization reaction with the fatty acid of the vegetable oil.
The first step is a step of reforming terminals of a diene-based polymer with functional groups.
The properties of the diene-based polymer depend largely on the positions of ?C=C- double bonds existing in the repeating units of polymer chains, the microstructure indicating the stereochemical properties, and the macrostructure indicating the branching, the molecular weight and the molecular weight distribution.
The diene-based polymer has different kinds of microstructures in terms of the molecular. structure. Different types of copolymers exist in the diene-based polymer. This makes it possible to produce elastomers having different physical properties.
In the present method, examples of the diene-based polymer include styrene butadiene rubber (SBR), butadiene rubber (BR) and styrene butadiene styrene (SBS). It is preferable to use styrene butadiene rubber as the diene-based polymer. The diene-based polymer can be produced by a polymerizing method ordinarily used in the art. For instance, if styrene butadiene rubber is used as the diene-based polymer, the styrene butadiene rubber can be polymerized to have a desired molecular weight by adding n-butyllithium catalyst to styrene monomers and butadiene monomers. However, the present invention is not limited thereto.
At this time, the styrene butadiene rubber may contain styrene monomers and butadiene monomers in different weight ratios, preferably in a weight ratio of 25:75.
In the present method, the diene-based polymer has a molecular weight of 10,000 or more, preferably a molecular weight of 10,000 to 100,000.
As an example, the styrene butadiene rubber having a molecular weight of 10,000 or more can be produced by putting styrene monomers and butadiene monomers into an autoclave in a weight ratio of 25:75, adding n-butyllithium as an initiator and polymerizing the styrene monomers and the butadiene monomers.
In the present method, the terminals of the diene-based polymer can be reformed different kinds of functional groups. As the functional groups, it is possible to use amino groups, hydroxyl groups, carboxyl groups and so forth. However, the present invention is not limited thereto.
A method known in the art can be used in reforming the terminals of the diene-based polymer with the functional groups. As an example, the terminals of the diene-based polymer can be reformed with amino groups through the use of 4-bromo-N,N-bis(trimethylsilyl)aniline.
The second step is a step of obtaining fatty acid by purifying waste vegetable oil. In the second step, the waste vegetable oil may be selected from the group consisting of soybean oil, sunflower oil and palm oil. However, the present invention is not limited thereto.
Referring to Figs. 13 and 14, the 1H-NMR analysis and the FT-IR analysis reveal that the waste vegetable oil is composed of triglyceride. As shown in Figs. 15, the 1H-NMR analysis reveals that the fatty acid obtained by filtering and purifying the waste vegetable oil is unsaturated hydrocarbon whose terminals are composed of carboxyl groups. Accordingly, the fatty acid can be easily coupled to the terminals of the diene-based polymer reformed by the functional groups.
In the present method, the fatty acid can be obtained from waste vegetable oil. Alternatively, it is possible to use commercially available fatty acid or fatty acid synthesized according to a method well-known in the art.
In the present method, the waste vegetable oil can be purified by a method ordinarily used in the art. However, the present invention is not limited thereto.
The third step is a step of producing a biomass elastomer by subjecting the diene-based polymer, the terminals of which are reformed by the functional groups in the second step, to polymerization reaction with the fatty acid of the waste vegetable oil.
The polymerization reaction can be performed within an autoclave preferably at a reaction temperature of 200 to 250℃.
The vegetable-oil-based biomass elastomer according to the present invention is produced by using a biomass, one of recyclable organic resources, as a raw material, combining the biomass with diene-based polymer and reforming the terminals of the diene-based polymer with functional groups. This makes it possible to produce a natural-substance-based environment-friendly recyclable elastomer having superior critical performance. The vegetable-oil-based biomass elastomer according to the present invention can be widely used in different industrial fields such as a medical field, a footwear material field, a car component material field and an electric and electronic component material field.
Next, the present invention will be described in detail by virtue of examples. These examples are presented merely for the sake of describing the present invention in more detail and are not intended to limit the scope of the present invention.
<Example 1> Production of SBS/Waste-Vegetable-Oil-Based Biomass Elastomer
Production of a biomass elastomer was started at a temperature of 40℃ by using cyclohexane as a solvent and using n-butyllithium as an initiator. 380 ml of cyclohexane was heated to 40℃. 25 ml of styrene monomers were added to the heated cyclohexane. Then, 3 ml of n-butyllithium and 70 g of butadiene monomers were added to the heated cyclohexane in the named order. 25 ml of styrene monomers was added to the solvent containing the butadiene monomers, thereby producing a styrene-butadiene-styrene (SBS) block copolymer. 3 g of waste soybean oil was added to the SBS block copolymer thus produced, consequently subjecting the SBS block copolymer and the waste soybean oil to coupling reaction. 5 ml of methyl alcohol as a reaction terminator was added to stop the coupling reaction, thus producing a biomass elastomer.
The reaction process for producing the biomass elastomer of example 1 is as follows (reaction formulae 1 to 4).
Reaction Formula 1: Reaction of Styrene and n-Butyllithium
[Rectified under Rule 91 21.08.2013]
Figure WO-DOC-FIGURE-88
Reaction Formula 2: Formation of Styrene-Butadiene Di-block Copolymer
[Rectified under Rule 91 21.08.2013]
Figure WO-DOC-FIGURE-90
Reaction Formula 3: Formation of Styrene-Butadiene-Styrene Tri-block Copolymer
[Rectified under Rule 91 21.08.2013]
Figure WO-DOC-FIGURE-92
Reaction Formula 4: Formation of Styrene-Butadiene-Styrene/Waste-Vegetable-Oil-Based Biomass Elastomer
[Rectified under Rule 91 21.08.2013]
Figure WO-DOC-FIGURE-94
<Test Example 1> Use of Styrene-Butadiene-Styrene/Waste-Vegetable-Oil-Based Biomass Elastomer
<1-1> GPC Analysis
Gel Permeation Chromatography (GPC) tests were conducted in order to find out the molecular weight of the biomass elastomer produced in example 1.
Fig. 1 shows a GPC analysis result of a pure SBS block copolymer. Fig. 2 shows a GPC analysis result of the biomass elastomer produced in example 1 (the SBS/waste-vegetable-oil-based biomass elastomer). The GPC analysis result shown in Fig. 1 is directed to a pure SBS block copolymer having a molecular weight of 25,000. The GPC analysis result shown in Fig. 2 is directed to a SBS/waste-vegetable-oil-based biomass elastomer having a molecular weight of 50,000.
Comparing Figs. 1 and 2, it can be noted that the molecular weight was twice increased from 25,000 to 50,000. This means that the vegetable oil and the copolymer are bonded to each other by divalent reaction. In other words, vegetable oil (structurally the same as triglyceride) is formed of three chains. It can be appreciated that coupling reaction has occurred in two chains.
<1-2> 1H-NMR Analysis
1H-Nuclear Magnetic Resonance (NMR) tests were conducted in order to find out the molecular structure of the biomass elastomer produced in example 1.
Fig. 3 shows a 1H-NMR analysis result of a pure SBS block copolymer. Fig. 4 shows a 1H-NMR analysis result of the biomass elastomer produced in example 1 (the SBS/waste-vegetable-oil-based biomass elastomer).
Comparing Figs. 3 and 4, unlike the SBS block copolymer, a new peak appears in Fig. 4 at about 3.6 ppm. This means that the SBS block copolymer and the vegetable oil are coupled to each other whereby the -C=O double bonds of the vegetable oil are converted to -C-O- single bonds.
<1-3> Physical Property Analysis
Tests for comparing the physical properties of the SBS block copolymer and the SBS/waste-vegetable-oil-based biomass elastomer were conducted. The results are shown in Table 1.
Table 1
sample Tensile strength(MPa) Elongation at break(%) Modulus at 100%(MPa) Modulus at 200%(MPa) Modulus at 300%(MPa) Hardness(°) Reality S:B(w/w)
SBS Mw=25000(S:B=3:7) 5.8 731 1.6 1.9 2.4 38 2.7:7.3
SBS Mw=25000(S:B=5:5) 10.8 436 5.7 7.1 8.5 80 4.5:5.5
SBS Mw=50000(S:B=3:7) 9.9 671 3.3 4.2 5.2 51 2.7:7.3
SBS Mw=50000(S:B=5:5) 14.5 484 7.1 8.4 10.4 87 4.5:5.5
SBS+Waste oil(S:B=3:7) 4.2 606 1.5 1.7 2.2 30 2.6:7.4
SBS+Waste oil(S:B=5:5) 7.0 330 3.3 3.7 4.0 69 4.4:5.6
SBS:Waste oil=1:1(molar ratio), MW of SBS is 25,000Reality S:B(w/w) is calculated by 1HNMR data
<Example 2> Production of SB-Block-Polymer/Waste-Vegetable-Oil-Based Biomass Elastomer
Production of a biomass elastomer was started at a temperature of 40℃ by using cyclohexane as a solvent and using n-butyllithium as an initiator. 380 ml of cyclohexane was heated to 40℃. 50 ml of styrene monomers were added to the heated cyclohexane. Then, 3 ml of n-butyllithium and 70 g of butadiene monomers were added to the heated cyclohexane in the named order, thereby producing a styrene-butadiene (SB) block polymer. 3 g of waste soybean oil was added to the SB block polymer thus produced, consequently subjecting the SB block polymer and the waste soybean oil to coupling reaction. 5 ml of methyl alcohol as a reaction terminator was added to stop the coupling reaction, thus producing a biomass elastomer.
The reaction process for producing the biomass elastomer of example 2 is as follows ( reaction formulae 1, 2 and 5).
Reaction Formula 1: Reaction of Styrene and n-Butyllithium
[Rectified under Rule 91 21.08.2013]
Figure WO-DOC-FIGURE-114
Reaction Formula 2: Formation of Styrene-Butadiene Di-block polymer
[Rectified under Rule 91 21.08.2013]
Figure WO-DOC-FIGURE-116
Reaction Formula 5: Formation of Styrene-Butadiene-Di-block-Polymer/Waste-Vegetable-Oil-Based Biomass Elastomer
[Rectified under Rule 91 21.08.2013]
Figure WO-DOC-FIGURE-118
<Test Example 2> Use of SB-Block-Polymer/Waste-Vegetable-Oil-Based Biomass Elastomer
<2-1> GPC Analysis
Gel Permeation Chromatography (GPC) tests were conducted in order to find out the molecular weight of the biomass elastomer produced in example 2.
Fig. 5 shows a GPC analysis result of a pure SB block polymer. Fig. 6 shows a GPC analysis result of the biomass elastomer produced in example 2 (the SB-block-polymer/waste-vegetable-oil-based biomass elastomer). The GPC analysis result shown in Fig. 5 is directed to a pure SB block polymer having a molecular weight of 25,000. The GPC analysis result shown in Fig. 6 is directed to a SB-block-polymer/waste-vegetable-oil-based biomass elastomer having a molecular weight of 50,000.
Comparing Figs. 5 and 6, it can be noted that the molecular weight was twice increased from 25,000 to 50,000. This means that the vegetable oil and the polymer are bonded to each other by divalent reaction. In other words, vegetable oil (structurally the same as triglyceride) is formed of three chains. It can be appreciated that coupling reaction has occurred in two chains.
<2-2> 1H-NMR Analysis
1H-Nuclear Magnetic Resonance (NMR) tests were conducted in order to find out the molecular structure of the biomass elastomer produced in example 2.
Fig. 7 shows a 1H-NMR spectrum of a pure SB block polymer. Fig. 8 shows a 1H-NMR analysis result of the biomass elastomer produced in example 2 (the SB-block-polymer/waste-vegetable-oil-based biomass elastomer).
Comparing Figs. 7 and 8, unlike the SB block polymer, a new peak appears in Fig. 8 at about 3.6 ppm. This means that the SB block polymer and the vegetable oil are coupled to each other whereby the -C=O double bonds of the vegetable oil are converted to -C-O- single bonds.
<2-3> Physical Property Analysis
Tests for comparing the physical properties of the SB block polymer and the SB-block-polymer/waste-vegetable-oil-based biomass elastomer were conducted. The results are shown in Table 2.
Table 2
unvulcanized
Sample Tensile strength(MPa) Elongation at break(%) Modulus at 100% Modulus at 200% Modulus at 300% Hardness(°) Reality S:B(w/w)
SB Mw=25000(S:B=3:7) 1.9 26 28 2.8:7.2
SB Mw=25000(S:B=5:5) 1.9 12 45 4.6:5.4
SB Mw=50000(S:B=3:7) 3.3 207 1.6 3.0 41 2.7:7.3
SB Mw=50000(S:B=5:5) 6.9 43 79 4.4:5.6
SB+Waste oil(S:B=3:7) 3.8 626 2.1 2.5 2.8 37 2.5:7.5
SB+Waste oil(S:B=5:5) 5.8 409 3.5 4.0 4.6 67 4.5:5.5
SB:Waste oil=1:1(molar ratio), Mw of SB is 25,000Reality S:B(w/w) is calculated by 1HNMR data
In order to compare the rheological properties of the SB block polymer and the SB-block-polymer/waste-vegetable-oil-based biomass elastomer, the maximum torque, the scorch time and the curing time were measured with a rheometer. The results are shown in Table 3.
[Rectified under Rule 91 21.08.2013]
Figure WO-DOC-TABLE-3
<Example 3> Production of SB-Random-Polymer/Waste-Vegetable-Oil-Based Biomass Elastomer
Production of a biomass elastomer was started at a temperature of 40℃ by using cyclohexane as a solvent and using n-butyllithium as an initiator. 50 ml of styrene monomers and 70 g of butadiene monomers were added to 380 ml of cyclohexane. The mixture was heated to 40℃. Then, 3 ml of n-butyllithium were added to the heated mixture, thereby producing a styrene-butadiene (SB) random polymer. 3 g of waste soybean oil was added to the SB random polymer thus produced, consequently subjecting the SB random polymer and the waste soybean oil to coupling reaction. 5 ml of methyl alcohol as a reaction terminator was added to stop the coupling reaction, thus producing a biomass elastomer.
The reaction process for producing the biomass elastomer of example 3 is as follows (reaction formulae 6 and 7).
Reaction Formula 6: Formation of Styrene-Butadiene Random Polymer
[Rectified under Rule 91 21.08.2013]
Figure WO-DOC-FIGURE-141
Reaction Formula 7: Formation of Styrene-Butadiene-Random-Polymer/Waste-Vegetable-Oil-Based Biomass Elastomer
[Rectified under Rule 91 21.08.2013]
Figure WO-DOC-FIGURE-143
<Test Example 3> Use of SB-Random-Polymer/Waste-Vegetable-Oil-Based Biomass Elastomer
<3-1> GPC Analysis
Gel Permeation Chromatography (GPC) tests were conducted in order to find out the molecular weight of the biomass elastomer produced in example 3.
Fig. 9 shows a GPC analysis result of a pure SB random polymer. Fig. 10 shows a GPC analysis result of the biomass elastomer produced in example 3 (the SB-random-polymer/waste-vegetable-oil-based biomass elastomer). The GPC analysis result shown in Fig. 9 is directed to a pure SB random polymer having a molecular weight of 25,000. The GPC analysis result shown in Fig. 10 is directed to a SB-random-polymer/waste-vegetable-oil-based biomass elastomer having a molecular weight of 50,000.
Comparing Figs. 9 and 10, it can be noted that the molecular weight was twice increased from 25,000 to 50,000. This means that the vegetable oil and the polymer are bonded to each other by divalent reaction. In other words, vegetable oil (structurally the same as triglyceride) is formed of three chains. It can be appreciated that coupling reaction has occurred in two chains.
<3-2> 1H-NMR Analysis
1H-Nuclear Magnetic Resonance (NMR) tests were conducted in order to find out the molecular structure of the biomass elastomer produced in example 3.
Fig. 11 shows a 1H-NMR spectrum of a pure SB random polymer. Fig. 12 shows a 1H-NMR analysis result of the biomass elastomer produced in example 3 (the SB-random-polymer/waste-vegetable-oil-based biomass elastomer).
Comparing Figs. 11 and 12, unlike the SB random polymer, a new peak appears in Fig. 12 at about 3.6 ppm. This means that the SB random polymer and the vegetable oil are coupled to each other whereby the -C=O double bonds of the vegetable oil are converted to -C-O- single bonds.
<3-3> Physical Property Analysis
In order to compare the rheological properties of the SB random polymer and the SB-random-polymer/waste-vegetable-oil-based biomass elastomer, the maximum torque, the scorch time and the curing time were measured with a rheometer. The results are shown in Table 4.
Table 4
Rheometer data SB random copolymer
Test Temperature ; 170℃
Sample MH ts2 tc50 tc90
SBR Mw=25000(S:B=3:7) 6.4 15.97 16.87 19.03
SBR Mw=25000(S:B=5:5) 4.2 19.92 20.03 24.58
SBR Mw=50000(S:B=3:7) 14.2 15.03 16.48 18.28
SBR Mw=50000(S:B=5:5) 10.3 18.22 19.65 22.77
SBR/waste oil(S:B=3:7) 5.6 9.37 9.85 13.25
SBR/waste oil(S:B=5:5) 4.6 14.12 14.33 18.15
<Example 4> Production of SB-Block-Polymer/Waste-Vegetable-Oil-Based Biomass Elastomer (Vulcanized)
100 g of the biomass elastomer produced in example 2, 5.0 g of zinc oxide, 1.5 g of stearic acid, 1.0 g of BHT, 1.25 g of sulfur and 2.0 g of CBS were mixed and subjected to heat treatment at a temperature of 160 to 170℃, thereby producing a biomass elastomer.
Tests for comparing the physical properties of the SB block polymer and the vulcanized SB-block-polymer/waste-vegetable-oil-based biomass elastomer were conducted. The results are shown in Table 5.
Table 5
Sample Tensile strength(MPa) Elongation at break(%) Modulus at 100% Modulus at 200% Modulus at 300% Hardness(°) Reality S:B(w/w)
SB Mw=25000(S:B=3:7) 5.4 244 2.7 4.5 55 2.8:7.2
SB Mw=25000(S:B=5:5) 10.0 196 7.6 85 4.6:5.4
SB Mw=50000(S:B=3:7) 7.9 454 2.4 3.8 5.6 61 2.7:7.3
SB Mw=50000(S:B=5:5) 12.4 285 10.4 11.6 88 4.4:5.6
SB+waste oil(S:B=3:7) 6.7 485 2.5 4.0 5.1 46 2.5:7.5
SB+waste oil(S:B=5:5) 11.0 294 7.1 10.2 71 4.5:5.5
SB:waste oil = 1:1(molar ratio), Mw of SB is 25000Reality S:B(w/w) is calculated by 1HNMR data<vulcanized> Formular = polymer;100, ZnO;5.0, SA;1.5, BHT;1.0, S;1.25, CBS;2.0
< Example 5> Production of SB - Random - Polymer / Waste - Vegetable - Oil - Based Biomass Elastomer ( Vulcanized )
100 g of the biomass elastomer produced in example 3, 5.0 g of zinc oxide, 1.5 g of stearic acid, 1.0 g of BHT, 1.25 g of sulfur and 2.0 g of CBS were mixed and subjected to heat treatment at a temperature of 160 to 170℃, thereby producing a biomass elastomer.
Tests for comparing the physical properties of the SB random polymer and the vulcanized SB-random-polymer/waste-vegetable-oil-based biomass elastomer were conducted. The results are shown in Table 6.
Table 6
Sample Tensile strength(MPa) Elongation at break(%) Modulus at 100% Modulus at 200% Modulus at 300% Hardness(°) Reality S:B(w/w)
SBR Mw=25000(S:B=3:7) 0.83 534 0.37 0.44 0.52 4 2.8:7.2
SBR Mw=25000(S:B=5:5) 1.56 638 0.51 0.61 0.71 6 4.6:5.4
SBR Mw=50000(S:B=3:7) 1.02 410 0.52 0.67 0.81 13 2.7:7.3
SBR Mw=50000(S:B=5:5) 2.40 569 0.68 0.88 1.09 17 4.4:5.6
SBR+waste oil(S:B=3:7) 0.86 576 0.30 0.38 0.46 3 2.5:7.5
SBR+waste oil(S:B=5:5) 1.12 648 0.40 0.46 0.54 5 4.5:5.5
SBR:waste oil = 1:1(molar ratio), Mw of SBR is 25000Reality S:B(w/w) is calculated by 1HNMR data<vulcanized> Formular = polymer;100, ZnO;5.0, SA;1.5, BHT;1.0, S;1.25, CBS;2.0
< Example 6> Production of Waste - Vegetable - Oil - Based Environment -Friendly Biomass Elastomer
First Step: Reforming of Terminals of Styrene-Butadiene Rubber
(1) Polymerization of Styrene-Butadiene Rubber
[Rectified under Rule 91 21.08.2013]
Figure WO-DOC-FIGURE-172
Styrene monomers, butadiene monomers and n-butyllithium as an initiator were put into an autoclave and are subjected to polymerization reaction. At this time, the styrene monomers and the butadiene monomers were added in a weight ratio of 25:75, thereby producing styrene-butadiene rubber.
(2) Reforming of Terminals of Styrene-Butadiene Rubber
[Rectified under Rule 91 21.08.2013]
Figure WO-DOC-FIGURE-175
4-bromo-N,N-bis(trimethylsilyl)aniline was added to the styrene-butadiene rubber produced in polymerization step (1). The mixture was stirred for three hours. Thereafter, a solution of 10% HCl/MeOH and 10% NaOH was added to the mixture. Then, the bis(trimethylsilyl) existing at the terminals was substituted by hydrogen (H) and was neutralized with NaOH. Thereafter, the reaction product was quenched with MeOH in an autoclave, thus removing and precipitating impurities. The solvent was evaporated by an evaporator. Then, moistures and impurities were completely evaporated and removed under a vacuum pressure in a vacuum drying oven, eventually reforming the terminals of the styrene-butadiene rubber with NH2.
Second Step: Separation of Fatty Acid from Waste Vegetable Oil
Waste vegetable oil was treated with methanol to separate fatty acid and waste glycerol. At this time, the waste glycerol was used to separate glycerol (95%) and fatty acid (5%). To this end, the waste glycerol and water were filled into a beaker in a ratio of 4:1 and were stirred by a stirrer. Then, the pH of the mixture was adjusted by adding 35.0% of HCl little by little. While stirring the mixture, sampling was performed by a pH meter and the pH of the mixture measured by pH paper was adjusted to become equal to 3. After precipitation reaction, fatty acid was obtained from the waste vegetable oil.
Third Step: Production of Biomass Elastomer
[Rectified under Rule 91 21.08.2013]
Figure WO-DOC-FIGURE-180
The styrene-butadiene rubber obtained in the first step, the terminals of which are reformed with NH2, and the fatty acid obtained in the second step were put into an autoclave and were subjected to reaction for three hours at a temperature of 200 to 250℃, thereby producing a biomass elastomer.
The 1H-NMR spectrum of the environment-friendly biomass elastomer thus produced is shown in Fig. 16. It can be appreciated in Fig. 16 that the styrene-butadiene rubber and the fatty acid are well coupled to each other in the biomass elastomer.
While certain preferred embodiments of the invention have been described hereinabove, it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the essential features of the invention. Accordingly, the embodiments disclosed herein shall be regarded as descriptive and not restrictive. The scope of the present invention shall be defined by the claims and not by the foregoing description. All equivalents shall be construed to fall within the scope of the present invention.
The vegetable-oil-based biomass elastomer produced by the present method can be widely used, as a hybrid material of petrochemical substance and natural substance capable of substituting a petroleum-derived polymer material, in different industrial fields such as a medical field, a footwear material field, a car component material field and an electric and electronic component material field.

Claims (17)

  1. A method of producing a vegetable-oil-based biomass elastomer, comprising:
    a step of producing a polymer selected from the group consisting of a styrene-butadiene-styrene block copolymer, a styrene-butadiene block polymer and a styrene-butadiene random polymer; and
    a step of adding vegetable oil to the polymer and subjecting the polymer and the vegetable oil to coupling reaction.
  2. The method of claim 1, further comprising:
    a step of mixing zinc oxide (ZnO), stearic acid, an antioxidant, sulfur (S) and a vulcanizing accelerator with the biomass elastomer obtained after the coupling reaction and vulcanizing the biomass elastomer.
  3. The method of claim 1, wherein, in the step of adding vegetable oil, the polymer and the vegetable oil are mixed in a molar ratio of 1:0.2 to 3.
  4. The method of claim 1, wherein the step of adding vegetable oil is performed for 30 to 140 minutes at a temperature of 25 to 55℃.
  5. The method of claim 1, wherein the styrene-butadiene-styrene block copolymer is produced by a method comprising the steps of: heating a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane to a temperature of 35 to 45℃; adding 30 to 70 wt% of styrene monomers on the basis of the total amount of the styrene monomers to be used to the heated solvent; adding an initiator to the solvent added with the styrene monomers and then adding butadiene monomers to the solvent; and adding the remaining 30 to 70 wt% of the styrene monomers to the solvent added with the butadiene monomers.
  6. The method of claim 1, wherein the styrene-butadiene block polymer is produced by a method comprising the steps of: heating a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane to a temperature of 35 to 45℃; adding styrene monomers to the heated solvent; and adding an initiator to the solvent added with the styrene monomers and then adding butadiene monomers to the solvent.
  7. The method of claim 1, wherein the styrene-butadiene random polymer is produced by a method comprising the steps of: adding styrene monomers and butadiene monomers to a hydrocarbon solvent selected from the group consisting of n-hexane, n-heptane, isooctane, cyclohexane and methylcyclopentane and heating the solvent to a temperature of 35 to 45℃; and adding an initiator to the heated solvent.
  8. A vegetable-oil-based biomass elastomer produced by the method of any one of claims 1 to 7.
  9. A method of producing a vegetable-oil-based biomass elastomer, comprising:
    a step (first step) of reforming terminals of a diene-based polymer with functional groups;
    a step (second step) of obtaining fatty acid by purifying vegetable oil; and
    a step (third step) of producing a biomass elastomer by subjecting the diene-based polymer, the terminals of which are reformed by the functional groups in the first step, to polymerization reaction with the fatty acid of the vegetable oil.
  10. A method of producing a vegetable-oil-based biomass elastomer, comprising:
    a step (first step) of reforming terminals of a diene-based polymer with functional groups; and
    a step (second step) of producing a biomass elastomer by subjecting the diene-based polymer, the terminals of which are reformed by the functional groups in the first step, to polymerization reaction with fatty acid.
  11. The method of claim 9 or 10, wherein the diene-based polymer is selected from the group consisting of styrene butadiene rubber, butadiene rubber and styrene butadiene styrene rubber.
  12. The method of claim 11, wherein the styrene butadiene rubber contains styrene monomers and butadiene monomers in a weight ratio of 25:75.
  13. The method of claim 9 or 10, wherein the diene-based polymer has a molecular weight of 10,000 to 100,000.
  14. The method of claim 9 or 10, wherein the functional groups include amino groups, hydroxyl groups and carboxyl groups.
  15. The method of claim 9 or 10, wherein, in the first step, the terminals of the diene-based polymer is reformed with amino groups through the use of 4-bromo-N,N-bis(trimethylsilyl)aniline.
  16. The method of claim 9 or 10, wherein the polymerization reaction of the diene-based polymer, the terminals of which are reformed by the functional groups in the first step, with the fatty acid is performed at a temperature of 200 to 250℃.
  17. A vegetable-oil-based biomass elastomer produced by the method of claim 9 or 10.
PCT/KR2013/003893 2012-10-02 2013-05-06 Method of producing vegetable-oil-based biomass elastomer and elastomer produced by the method WO2014054846A1 (en)

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