WO2023129067A1 - A polymeric material for preserving the freshness of food products - Google Patents

A polymeric material for preserving the freshness of food products Download PDF

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Publication number
WO2023129067A1
WO2023129067A1 PCT/TR2022/051638 TR2022051638W WO2023129067A1 WO 2023129067 A1 WO2023129067 A1 WO 2023129067A1 TR 2022051638 W TR2022051638 W TR 2022051638W WO 2023129067 A1 WO2023129067 A1 WO 2023129067A1
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Prior art keywords
polymeric material
nanocomposite
material according
nanocomposite polymeric
polyurethane
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PCT/TR2022/051638
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French (fr)
Inventor
Serkan Unal
Hayriye Unal
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Sabanci Üniversitesi
Sabanci Üniversitesi Nanoteknoloji Arastirma Ve Uygulama Merkezi Sunum
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Priority claimed from TR2021/021440 external-priority patent/TR2021021440A2/en
Application filed by Sabanci Üniversitesi, Sabanci Üniversitesi Nanoteknoloji Arastirma Ve Uygulama Merkezi Sunum filed Critical Sabanci Üniversitesi
Publication of WO2023129067A1 publication Critical patent/WO2023129067A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
    • C08J9/008—Nanoparticles
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/144—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23B7/152—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere comprising other gases in addition to CO2, N2, O2 or H2O ; Elimination of such other gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • 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
    • C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the present invention relates to a nanocomposite polymeric material comprising at least one polymeric component and nanoclay particles.
  • the present invention relates to polymeric materials that are used to preserve the freshness of food products such as fresh fruits and vegetables, and a production method thereof.
  • Food products such as fruits and vegetables are stored in packages or in sealed environments during the storage period.
  • the quality of the food is directly affected by the physical conditions of the environment they are kept.
  • ethylene gas i.e., phytohormone.
  • Ethylene is a gaseous plant growth hormone.
  • Even low concentrations of ethylene promote the growth of plants and the ripening of food products.
  • ethylene affects the food product from which it is released, while also spreading in the form of a gas in its environment and affecting the adjacent food products.
  • unripened food products that are stored with ripened ones exhibit fast ripening.
  • the effect of ethylene gas on ripening process leads to undesirable results.
  • fruits and vegetables ripe the amount of ethylene gas they release increases.
  • a reduction in the ambient temperature reduces the effects of ethylene gas emission, but it may have a negative effect on the organoleptic behavior of the food products.
  • the maximum temperature to which the temperature of the product can be reduced may be close to the freezing temperature. Such limited cooling is insufficient to ensure the desired protective effect.
  • WO 2005/000369 Al and EP 0 515 764 A2 suggest the use of potassium permanganate in order to remove the effects of ethylene gas.
  • potassium permanganate is a component that is not used in Europe anymore due to its toxicity; therefore, it is not preferred in food products.
  • the food components that are treated with certain chemical compounds preserve their structure for a longer period of time, but processed food products are not preferred by consumers.
  • the amount of moisture in the atmosphere being in contact with the food is important in preserving the freshness of the food products and ensuring microbial quality.
  • Isolating food products from the external environment reduces the risk of contamination originating therefrom, but there have been problems that reduce the quality of the product in the packaging or in the sealed environment where it is stored.
  • Principal object of the present invention is to provide materials that help preserving the freshness and product quality of the food products such as fruits and vegetables for a long period of time.
  • Another object of the present invention is to eliminate the negative effects of ethylene gas formed in sealed areas or in packages where the food products are stored. Another object of the present invention is to eliminate the negative effects of moisture in sealed areas or in packages where the food products are stored.
  • Another object of the present invention is to provide a low-cost material that is ease- to-manufacture.
  • Another object of the present invention is to provide a material that is resistant against environmental factors and external effects.
  • Yet another object of the present invention is to provide a material that provides a practical application and does not take up much space.
  • the present invention describes a nanocomposite polymeric material comprising at least one polymeric component and nanoclay particles, wherein said material is porous and the material further comprises a thickening agent, a foaming agent, or a combination thereof.
  • the present invention describes a method for obtaining a nanocomposite polymeric material, wherein said method comprises the steps of preparing a polymeric dispersion from the at least one polymeric component, foaming said polymeric dispersion by mixing it with the thickening agent and the foaming agent, and then adding nanoclay particles to the foamed dispersion, and mixing same.
  • the present invention describes a use of said nanocomposite polymeric material in the absorption of the ethylene gas and moisture in the environment.
  • the present invention describes a use of said nanocomposite polymeric material as a material to preserve the freshness of the fresh fruits and vegetables.
  • the present invention describes a use of said nanocomposite polymeric material in the form of a foam.
  • the present invention describes a use of said nanocomposite polymeric material in the form of a pad.
  • the present invention provides a nanocomposite polymeric material comprising at least one polymeric component and nanoclay particles.
  • said material is porous and the material further comprises a thickening agent, a foaming agent, or a combination thereof.
  • the nanoclay particles in the polymeric composition it has been possible to effectively absorb the undesirable ethylene gas produced by the food products such as fresh fruits and vegetables.
  • Ethylene gas that causes a fast ripening of the fruits and vegetables if the environment is not sufficiently ventilated and the resulting ethylene gas is not removed, causes a decrease in the nutritional value of the products and even the deterioration thereof, during the transportation and/or storage of the food products.
  • the nanoclay particles in the polymeric material can absorb ethylene gas effectively, thereby eliminating the negative situations caused by ethylene gas.
  • the moisture in the environment where the food products such as fresh fruits and vegetables are kept is also absorbed, thus eliminating the harmful effects of excess moisture in the environment.
  • the nanocomposite polymeric material comprising at least one polymeric component and nanoclay particles is porous.
  • the material should not contact with the ambient air. Due to the porous structure, moisture and undesirable gases can move through the nanocomposite polymeric material. The moisture and undesirable gases moving through the material are absorbed by the nanoclay particles and polymer matrix in the said material.
  • the polymer matrix mentioned herein may comprise at least one polymeric component as well as a thickening agent and/or a foaming agent. So, the negative effects of moisture and undesirable gases, such as ethylene gas, trapped in the nanoclay particles are prevented.
  • Said nanocomposite polymeric material also comprises a thickening agent, a foaming agent, or a combination thereof. These agents contribute to the physical properties of the material.
  • nanocomposite polymeric materials should be used in the environments where these food products are stored or transported. In cases where said food products are stored or transported in packaged form, said material should be kept in packages.
  • the polymeric material of the invention is expected to be durable and not affected by the ambient conditions such as temperature, humidity, impact, etc. immediately.
  • a thickening agent, a foaming agent or a combination thereof a nanocomposite polymeric material is obtained having high strength and high physical stability.
  • preferred polymers may be polyurethane, polyacrylate, polyester, epoxy, polyvinyl acetate, vinyl polymers, a mixture of copolymers containing at least one of a monomer of said polymers, or a combination thereof.
  • said polymeric component is a water-based polymer.
  • the polymeric component may be a molten polymer.
  • the polymeric component used in the nanocomposite polymeric material directly affects the properties of the resulting material; therefore, the choice of polymer is important.
  • a polymer matrix is obtained, and with the nanocomposite polymeric material made from the polymer matrix, undesirable gases and moisture produced by the food products such as fresh fruits and vegetables are absorbed. Therefore, there will be decrease in the concentration of undesirable gases such as ethylene gas in the environment, and thus, such conditions as decaying, deterioration, etc. of the food products will be eliminated.
  • moisture produced by the food products and the ambient conditions will be trapped by the nanocomposite polymeric material comprising the said polymer component, and the amount of moisture in the environment where the food products are placed will be reduced.
  • the polymeric component is polyurethane and said nanocomposite polymeric material is made of polyurethane.
  • the nanocomposite polymeric material In order for the nanocomposite polymeric material to maintain its structure for a long period of time and to absorb ethylene gas and moisture, it should not be affected by the ambient conditions such as temperature, humidity, pressure, etc. With the nanocomposite polymeric material made of polyurethane, both ethylene gas and moisture is effectively absorbed, and a material is obtained that is resistant to the ambient conditions.
  • a water-based polyurethane is preferred as the polymeric component.
  • the nanocomposite polymeric material made of the water-based urethane effectively absorbs the gas and moisture in the environment, thereby increasing the life of the food.
  • the polyurethane forming the polymer matrix in the nanocomposite polymeric material is obtained by polymerization of diisocyanate monomer, polyol, ionic or hydrophilic chain extender components.
  • a nonionic or non-hydrophilic chain extender can also be used.
  • the weight of the polyol in the polyurethane component used for obtaining the nanocomposite polymeric material is 60-90%, preferably 75-85%, by the total weight of the polyurethane.
  • the material of the invention it is aimed that the material has a hydrophilic character.
  • the hydrophilicity of the nanocomposite polymeric material i.e., the moisture-absorbing capacity, may be adjusted.
  • Preferred polyol compounds may be polyester, polyether, polydimethylsiloxane, polyacrylic, polybutadiene polyol, or a combination thereof.
  • the nanocomposite polymeric material to be used for those food products requiring a dry environment during the storage and transportation absorbs gas and moisture at the maximum rate, whereas the material to be used in food products requiring a more humid environment is required to absorb less gas and moisture.
  • the average particle diameter of the polyurethane particles used for obtaining the nanocomposite polymeric material is in the range of 50-900 nm, preferably in the range of 50-450 nm.
  • the average particle diameter of the polyurethane particles is measured by Dynamic Light Scattering (DLS) technique. As the particle size decreases within said ranges, the hydrophilicity of the material, and accordingly, its moisture absorbing capacity increases.
  • DLS Dynamic Light Scattering
  • the weight of the polymeric component is in the range of 35-75% by the weight of the nanocomposite polymeric material. In this way, optimum bending strength is achieved, therefore said nanocomposite polymeric material is minimally affected by the impacts during the transportation and storage of the food products such as fresh fruits and vegetables.
  • the total weight of the thickening agent and the foaming agent is in the range of 0.1-15% by weight of the nanocomposite polymeric material.
  • the nanoclay particles in the nanocomposite polymeric material are dispersed in the polymeric component.
  • the task of the nanoclay particles is to absorb ethylene gas and moisture in an effective manner, and at the same time to reduce their concentration in the environment. With the nanoclay particles being dispersed, a homogeneous dispersion is achieved in the polymeric component. In the homogeneous material, passage of gas and moisture is faster, thus undesirable gases and moisture produced by the food products such as fresh fruits and vegetables are absorbed in the most effective manner.
  • particles of halloysite, montmorillonite, sepiolite, cloisite, laponite, or a combination thereof are used as nanoclay particles. In this way, it is ensured that said nanocomposite polymeric material has ethylene retention properties.
  • the weight of the nanoclay particles used herein is in the range of 20-50%, preferably 25-35% by the total weight of the nanocomposite polymeric material.
  • Nanoclay particles in the material are components to trap undesirable gases and moisture. It has been observed that the amount of nanoclay particles in the nanocomposite polymeric material has direct effect on the ethylene gas and moisture absorbing capacity. In cases where nanoclay particles are used less than 20%, ethylene gas and moisture, which cause deterioration of the food products such as fresh fruits and vegetables, could not be absorbed sufficiently. In cases where said nanoclay particles are used more than 50%, a porous structure having the desired properties cannot be obtained, thereby making it difficult to obtain the foam structure.
  • the nanoclay particles are present in a range of 20-50% by the total weight of the material, in order for nanocomposite polymeric materials to be able to preserve the freshness of the food products by effectively absorbing undesirable gases such as ethylene gas and moisture and to have a long-term effect of the said material in ambient conditions.
  • the nanoclay particles are tubular.
  • the inner lumens, i.e., inner side, of the nanoclay particles are hollow.
  • the concentration of the ethylene gas and moisture in the environment of the food products is significantly decreased.
  • the freshness of the food products such as fresh fruits and vegetables can be preserved for a longer period of time.
  • halloysite nanotubes are used as nanoclay particles.
  • the inner lumens of the halloysite nanotubes used in the nanocomposite polymeric material are hollow.
  • Halloysite is a crystalline clay mineral from the kaolin group, which is available in nature, has a chemical structure of AI 2 [Si 2 O 5 (OH) 4 ].2H 2 O, and consists of two layers with silica on the outer surface and alumina on the inner surface.
  • the dimensions and shapes of halloysite clay mineral may vary according to the deposit and formation conditions, it may have various morphologies such as tubular, spherical or rod-like, mostly wide tubular form.
  • the halloysite particles used in the nanocomposite polymeric component obtained according to the invention are a natural material exhibiting no toxic effects.
  • nanocomposite polymeric material is in the form of foam.
  • the nanocomposite polymeric material being in the foam form, passage of the gas and moisture in the environment is accelerated, thereby ensuring the freshness of the food products such as fresh fruits and vegetables.
  • the nanocomposite polymeric material in the form of foam is light-weighted, the use of this material during the storage and transportation of the food products is easier.
  • the nanocomposite polymeric material may be in the form of pad.
  • the use of nanocomposite polymeric material in pad form is very advantageous. In addition to its resistance against physical impacts such as pressure, it is easily and in a very practical manner inserted into the packages where the food products such as fresh fruits and vegetables are stored.
  • the pores in the nanocomposite polymeric material allow the passage of ethylene gas and moisture through the material.
  • the polymeric material should be porous, so that undesirable gases and moisture can penetrate into the nanocomposite polymeric material and said components are absorbed effectively. In this way, it is observed that undesirable ethylene gas and excess moisture in the environment is significantly reduced. With the use of the porous nanocomposite polymeric material, it is observed that such formations as color change, deterioration, decay, etc. in the food products such as fresh vegetables and fruits are successfully prevented, enabling the food products remain fresh for a long period of time without deterioration in structure.
  • the foaming agent used for obtaining the nanocomposite polymeric material includes betaine, ammonium stearate, alkanol amide, sodium sulfosuccinate, alkyl-phenol ethoxylate, or a combination thereof.
  • said foaming agents By using said foaming agents, the polymer dispersion is foamed successfully, and it is ensured that the material in the form of a foam or pad retains this structure.
  • said agents depending on the hydrophilic groups contained therein, contribute to the moisture retention capability of the resulting nanocomposite polymeric material.
  • the thickening agent used for obtaining the nanocomposite polymeric material may be cellulosic, alkali-swellable emulsion (ASE), hydrophobically modified alkali-swellable emulsion (HASE) and hydrophobically modified ethoxylated urethane (HEUR), or a combination thereof. With the use of said thickening agents, it is ensured that the polymer dispersion foamed in liquid form still maintains its foam form in liquid form.
  • the foaming agent used in the nanocomposite polymeric material enables foaming of the polymeric component dispersion while the thickening agent contributes to a more consistent structure thereof.
  • the nanocomposite polymeric material should be porous and the size of said pores should be large enough to allow the passage of ethylene gas and moisture into the material.
  • the weight ratio of the foaming agent to thickening agent used herein is in the range of 0.5 - 3.0, preferably 1.0-2.0, it is observed that the diameter of the pores formed in the material ensures maximum ethylene gas and moisture absorption.
  • the dispersion of the polymeric component is prepared. At least one polymeric component is used in the preparation of the polymeric dispersion. Then, a thickening agent and a foaming agent are added to the polymeric component dispersion. Thus, the polymeric component dispersion is foamed.
  • a thickening agent and a foaming agent can be performed by any mixing method.
  • Nanoclay particles are added to the foamed dispersion. Once the nanoclay particles are added, they are mixed by any method and dispersed in the polymeric component dispersion. Said mixing method may include mechanical mixing processes. Preferably, high speed mixing method is used.
  • the nanoclay particles are added.
  • the particles are dispersed in the dispersion.
  • the mixing process mentioned herein may be a mechanical mixing method.
  • the polymeric dispersion is foamed by adding the thickening agent and the foaming agent.
  • the mixing processes performed herein can be performed by mechanical methods.
  • the polymeric component used for obtaining the nanocomposite polymeric material may preferably be polyurethane, polyacrylate, polyester, epoxy, polyvinyl acetate, vinyl polymers, as well as a polymer comprising a group, mixture of copolymers containing at least one of the monomers thereof, or a combination thereof.
  • polyurethane as the polymeric component, it is observed that the resulting nanocomposite polymeric material is more resistant against physical and environmental conditions.
  • a water-based polymer or a molten polymer is suitable to be used as the polymeric component.
  • a water-based polyurethane is used in the method for obtaining the nanocomposite polymeric material.
  • the nanocomposite polymeric material is used for a long period of time without deterioration in its structure and it is also desired that it is hydrophilic in order to effectively absorb undesirable gases and moisture in the environment.
  • a polyurethane that is obtained by polymerization of diisocyanate monomer, polyol, ionic or hydrophilic chain extender components is suitable to be used, and thus, it is seen that nanocomposite polymeric material having the desired properties is obtained.
  • a nonionic or non-hydrophilic chain extender can also be used for obtaining the polyurethane.
  • the nanoclay particles are dispersed in the polymeric component dispersion.
  • the average particle diameter of the particles which are in the form of a water-based dispersion of the polyurethane selected as the polymeric component, is in the range of 50-900 nm, preferably in the range of 50-450 nm.
  • the polymeric component dispersion in foam form comprising the nanoclay particles is brought into a pad form.
  • This can be performed by known conventional methods.
  • the polymeric component dispersion in foam form comprising the nanoclay particles is in foamed state due to the foaming agent and the thickening agent therein, so the polymeric dispersion is in the foam form.
  • a nanocomposite polymeric material in the form of a pad can be obtained from the foam form by known methods.
  • a nanocomposite polymeric material in the form of a foam can be obtained from the foamed polymeric dispersion by suitable methods.
  • the nanocomposite polymeric material in foam form is brought into pad form through a separate method step.
  • One of the methods that is suitable to be used is that the nanocomposite polymeric material in form foam can be brought into a pad form by subjecting it to die casting or film casting method.
  • the nanocomposite polymeric material of the invention is suitable to be used to absorb the ethylene gas and moisture in its environment.
  • the nanocomposite polymeric material used for preserving the freshness of fresh fruits and vegetables the ethylene gas and moisture in the environment of the said food products are removed from the environment and neutralized.
  • said food products can be stored for a long period of time while preserving their freshness.
  • the foam form of the nanocomposite polymeric material of the invention can be introduced into the environments where food products are stored, in a very practical manner.
  • the nanocomposite polymeric material used to absorb the ethylene gas and capture moisture is in the form of a pad. Thus, it can be introduced into the same environment with the food products during the transportation and storage of the food products, and neutralizes the ethylene gas and moisture in the environment.

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  • Organic Chemistry (AREA)
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Abstract

The present invention describes a nanocomposite polymeric material comprising at least one polymeric component and nanoclay particles, wherein said material is porous and the material further comprises a thickening agent, a foaming agent, or a combination thereof. The present invention describes a method for obtaining a nanocomposite polymeric material, wherein said method comprises the steps of preparing a polymeric dispersion from the at least one polymeric component, foaming said polymeric dispersion by mixing it with the thickening agent and the foaming agent, and then adding nanoclay particles to the foamed dispersion, and mixing same.

Description

A POLYMERIC MATERIAL FOR PRESERVING THE FRESHNESS OF FOOD PRODUCTS
Technical Field of the Invention
The present invention relates to a nanocomposite polymeric material comprising at least one polymeric component and nanoclay particles. In particular, the present invention relates to polymeric materials that are used to preserve the freshness of food products such as fresh fruits and vegetables, and a production method thereof.
Background Art
Food products such as fruits and vegetables are stored in packages or in sealed environments during the storage period. The quality of the food is directly affected by the physical conditions of the environment they are kept.
In particular, foods such as climacteric fruits and vegetables release ethylene gas, i.e., phytohormone. Ethylene is a gaseous plant growth hormone. Even low concentrations of ethylene promote the growth of plants and the ripening of food products. First of all, ethylene affects the food product from which it is released, while also spreading in the form of a gas in its environment and affecting the adjacent food products. For example, unripened food products that are stored with ripened ones exhibit fast ripening. In some cases, the effect of ethylene gas on ripening process leads to undesirable results. As fruits and vegetables ripe, the amount of ethylene gas they release increases. For example, food products such as fruits and vegetables in poorly ventilated environments or in packages tend to soften, spoil and decay after rapid ripening due to a high concentration of ethylene gas in the environment. The process resulting in staining, softening and eventually decaying of fruits and vegetables also affects the taste, smell and nutritional behavior of the food products. This significantly affects the quality of the food products that are packaged after harvesting or kept in a sealed environment, and even causes product losses in cases where ethylene gas cannot be sufficiently removed from the environment. It is an aim to preserve the quality of the food products packaged in this way or kept in sealed environments, and to prevent the deterioration thereof. In view of the above, some methods have been tried in order to protect food products from the negative effects of ethylene gas. A reduction in the ambient temperature reduces the effects of ethylene gas emission, but it may have a negative effect on the organoleptic behavior of the food products. On the other hand, the maximum temperature to which the temperature of the product can be reduced may be close to the freezing temperature. Such limited cooling is insufficient to ensure the desired protective effect.
WO 2005/000369 Al and EP 0 515 764 A2 suggest the use of potassium permanganate in order to remove the effects of ethylene gas. However, potassium permanganate is a component that is not used in Europe anymore due to its toxicity; therefore, it is not preferred in food products.
The food components that are treated with certain chemical compounds preserve their structure for a longer period of time, but processed food products are not preferred by consumers.
In addition to the water-vapor permeability of the environment in which the food products are placed, fresh food products such as fruits and vegetables contain water in their structure, consequently in time there occurs an increase in the moisture level of the atmosphere in the environment where such products are placed. If the resulting moisture cannot be removed from the environment, it remains in the said environment, causing problems such as temperature fluctuations and condensation. Particularly, in food products such as fresh fruits and vegetables interacting with water in an easy manner, excess moisture in any sealed storage environment, such as a packaging, not only reduces the quality of the product but also impairs the physical integrity of the environment, or the package, where the food products are stored.
In addition, an increase in the humidity of the environment accelerates the formation of bacteria and mold, which leads to a decrease in the nutritional value of the food. Although some moisture is required for the protection and preservation of the quality of the food products, an increase in moisture concentration has negative affect on the structure of the product. Therefore, it is important to control the humidity in the environment where food products are placed, in order to prevent microbial formation and to preserve the sensory properties of the food. A high moisture causes changes in the texture and appearance of the food products and reduces the shelf life.
The amount of moisture in the atmosphere being in contact with the food is important in preserving the freshness of the food products and ensuring microbial quality.
If the microbial growth, enzymatic activities, biochemical deterioration and moisture loss observed in food products is slowed down, it allows to offer higher quality food products to the consumer.
Isolating food products from the external environment reduces the risk of contamination originating therefrom, but there have been problems that reduce the quality of the product in the packaging or in the sealed environment where it is stored.
Therefore, it is important to eliminate the problems caused by ethylene gas and moisture formation during the storage and transportation of the food products.
For this reason, both the consumers and the food producers have focused on the systems that can prevent economic losses resulting from the deterioration of the food products due to the ethylene gas and moisture in the environment, as well as the health problems caused by the deteriorated food products. Therefore, there is a need for materials that, when in contact with the food products such as fruits and vegetables, are not inconvenient for human health, and that can effectively neutralize the ethylene gas and moisture formed in the environment.
Objects of the Invention
Principal object of the present invention is to provide materials that help preserving the freshness and product quality of the food products such as fruits and vegetables for a long period of time.
Another object of the present invention is to eliminate the negative effects of ethylene gas formed in sealed areas or in packages where the food products are stored. Another object of the present invention is to eliminate the negative effects of moisture in sealed areas or in packages where the food products are stored.
Another object of the present invention is to provide a low-cost material that is ease- to-manufacture.
Another object of the present invention is to provide a material that is resistant against environmental factors and external effects.
Yet another object of the present invention is to provide a material that provides a practical application and does not take up much space.
Summary of the Invention
The present invention describes a nanocomposite polymeric material comprising at least one polymeric component and nanoclay particles, wherein said material is porous and the material further comprises a thickening agent, a foaming agent, or a combination thereof.
The present invention describes a method for obtaining a nanocomposite polymeric material, wherein said method comprises the steps of preparing a polymeric dispersion from the at least one polymeric component, foaming said polymeric dispersion by mixing it with the thickening agent and the foaming agent, and then adding nanoclay particles to the foamed dispersion, and mixing same.
The present invention describes a use of said nanocomposite polymeric material in the absorption of the ethylene gas and moisture in the environment.
The present invention describes a use of said nanocomposite polymeric material as a material to preserve the freshness of the fresh fruits and vegetables.
The present invention describes a use of said nanocomposite polymeric material in the form of a foam.
The present invention describes a use of said nanocomposite polymeric material in the form of a pad.
Detailed Description of the Invention
The present invention provides a nanocomposite polymeric material comprising at least one polymeric component and nanoclay particles. In the nanocomposite polymeric material which is the subject of the invention, said material is porous and the material further comprises a thickening agent, a foaming agent, or a combination thereof.
With the nanoclay particles in the polymeric composition, it has been possible to effectively absorb the undesirable ethylene gas produced by the food products such as fresh fruits and vegetables. Ethylene gas that causes a fast ripening of the fruits and vegetables, if the environment is not sufficiently ventilated and the resulting ethylene gas is not removed, causes a decrease in the nutritional value of the products and even the deterioration thereof, during the transportation and/or storage of the food products. At this point, it is highly important to remove the ethylene gas in the environment or to neutralize it. In the invention, it is seen that the nanoclay particles in the polymeric material can absorb ethylene gas effectively, thereby eliminating the negative situations caused by ethylene gas. In addition to this effect, with the use of nanoclay particles in the nanocomposite polymeric material, the moisture in the environment where the food products such as fresh fruits and vegetables are kept is also absorbed, thus eliminating the harmful effects of excess moisture in the environment.
The nanocomposite polymeric material comprising at least one polymeric component and nanoclay particles is porous. In order for the said nanocomposite polymeric material to neutralize the moisture and undesirable gases in the environment, the material should not contact with the ambient air. Due to the porous structure, moisture and undesirable gases can move through the nanocomposite polymeric material. The moisture and undesirable gases moving through the material are absorbed by the nanoclay particles and polymer matrix in the said material. The polymer matrix mentioned herein may comprise at least one polymeric component as well as a thickening agent and/or a foaming agent. So, the negative effects of moisture and undesirable gases, such as ethylene gas, trapped in the nanoclay particles are prevented.
Said nanocomposite polymeric material also comprises a thickening agent, a foaming agent, or a combination thereof. These agents contribute to the physical properties of the material. In order to preserve the freshness of the food products such as fresh fruit and vegetables, nanocomposite polymeric materials should be used in the environments where these food products are stored or transported. In cases where said food products are stored or transported in packaged form, said material should be kept in packages. In order to have a long-term effect on ambient conditions, the polymeric material of the invention is expected to be durable and not affected by the ambient conditions such as temperature, humidity, impact, etc. immediately. By using a thickening agent, a foaming agent or a combination thereof, a nanocomposite polymeric material is obtained having high strength and high physical stability.
According to the invention, preferred polymers may be polyurethane, polyacrylate, polyester, epoxy, polyvinyl acetate, vinyl polymers, a mixture of copolymers containing at least one of a monomer of said polymers, or a combination thereof. In another embodiment of the invention, said polymeric component is a water-based polymer.
In another embodiment of the invention, the polymeric component may be a molten polymer.
The polymeric component used in the nanocomposite polymeric material directly affects the properties of the resulting material; therefore, the choice of polymer is important. Starting from the said polymeric components, a polymer matrix is obtained, and with the nanocomposite polymeric material made from the polymer matrix, undesirable gases and moisture produced by the food products such as fresh fruits and vegetables are absorbed. Therefore, there will be decrease in the concentration of undesirable gases such as ethylene gas in the environment, and thus, such conditions as decaying, deterioration, etc. of the food products will be eliminated. In addition, moisture produced by the food products and the ambient conditions will be trapped by the nanocomposite polymeric material comprising the said polymer component, and the amount of moisture in the environment where the food products are placed will be reduced.
In another preferred embodiment of the invention, the polymeric component is polyurethane and said nanocomposite polymeric material is made of polyurethane. In order for the nanocomposite polymeric material to maintain its structure for a long period of time and to absorb ethylene gas and moisture, it should not be affected by the ambient conditions such as temperature, humidity, pressure, etc. With the nanocomposite polymeric material made of polyurethane, both ethylene gas and moisture is effectively absorbed, and a material is obtained that is resistant to the ambient conditions.
In another preferred embodiment of the invention, a water-based polyurethane is preferred as the polymeric component. The nanocomposite polymeric material made of the water-based urethane effectively absorbs the gas and moisture in the environment, thereby increasing the life of the food.
According to another embodiment of the invention, the polyurethane forming the polymer matrix in the nanocomposite polymeric material is obtained by polymerization of diisocyanate monomer, polyol, ionic or hydrophilic chain extender components. In addition to the said elements, a nonionic or non-hydrophilic chain extender can also be used.
According to another embodiment of the invention, the weight of the polyol in the polyurethane component used for obtaining the nanocomposite polymeric material is 60-90%, preferably 75-85%, by the total weight of the polyurethane. In order for the material of the invention to effectively absorb the moisture and gas in the environment, it is aimed that the material has a hydrophilic character. According to the type and amount of polyol in the polyurethane, the hydrophilicity of the nanocomposite polymeric material, i.e., the moisture-absorbing capacity, may be adjusted. Preferred polyol compounds may be polyester, polyether, polydimethylsiloxane, polyacrylic, polybutadiene polyol, or a combination thereof. Therefore, it is desired that the nanocomposite polymeric material to be used for those food products requiring a dry environment during the storage and transportation, absorbs gas and moisture at the maximum rate, whereas the material to be used in food products requiring a more humid environment is required to absorb less gas and moisture. In view of the above requirement, it is highly important to adjust the gas- and moisture-absorbing capacity of the nanocomposite polymeric material.
According to another embodiment of the invention, the average particle diameter of the polyurethane particles used for obtaining the nanocomposite polymeric material is in the range of 50-900 nm, preferably in the range of 50-450 nm. The average particle diameter of the polyurethane particles is measured by Dynamic Light Scattering (DLS) technique. As the particle size decreases within said ranges, the hydrophilicity of the material, and accordingly, its moisture absorbing capacity increases.
According to another embodiment of the invention, the weight of the polymeric component is in the range of 35-75% by the weight of the nanocomposite polymeric material. In this way, optimum bending strength is achieved, therefore said nanocomposite polymeric material is minimally affected by the impacts during the transportation and storage of the food products such as fresh fruits and vegetables. According to another embodiment of the invention, the total weight of the thickening agent and the foaming agent is in the range of 0.1-15% by weight of the nanocomposite polymeric material.
According to another embodiment of the invention, the nanoclay particles in the nanocomposite polymeric material are dispersed in the polymeric component. The task of the nanoclay particles is to absorb ethylene gas and moisture in an effective manner, and at the same time to reduce their concentration in the environment. With the nanoclay particles being dispersed, a homogeneous dispersion is achieved in the polymeric component. In the homogeneous material, passage of gas and moisture is faster, thus undesirable gases and moisture produced by the food products such as fresh fruits and vegetables are absorbed in the most effective manner.
In another embodiment of the invention, particles of halloysite, montmorillonite, sepiolite, cloisite, laponite, or a combination thereof are used as nanoclay particles. In this way, it is ensured that said nanocomposite polymeric material has ethylene retention properties.
The weight of the nanoclay particles used herein is in the range of 20-50%, preferably 25-35% by the total weight of the nanocomposite polymeric material. Nanoclay particles in the material are components to trap undesirable gases and moisture. It has been observed that the amount of nanoclay particles in the nanocomposite polymeric material has direct effect on the ethylene gas and moisture absorbing capacity. In cases where nanoclay particles are used less than 20%, ethylene gas and moisture, which cause deterioration of the food products such as fresh fruits and vegetables, could not be absorbed sufficiently. In cases where said nanoclay particles are used more than 50%, a porous structure having the desired properties cannot be obtained, thereby making it difficult to obtain the foam structure. It is preferred that the nanoclay particles are present in a range of 20-50% by the total weight of the material, in order for nanocomposite polymeric materials to be able to preserve the freshness of the food products by effectively absorbing undesirable gases such as ethylene gas and moisture and to have a long-term effect of the said material in ambient conditions.
According to another embodiment of the invention, the nanoclay particles are tubular. In addition, it is preferred that the inner lumens, i.e., inner side, of the nanoclay particles are hollow. Thus, it has been observed that the ethylene gas and moisture, which are desired to be absorbed from the environment, are absorbed faster. On the other hand, in the event that nanoclay particles having hollow inner lumens are used, the concentration of the ethylene gas and moisture in the environment of the food products is significantly decreased. Thus, the freshness of the food products such as fresh fruits and vegetables can be preserved for a longer period of time.
According to a preferred embodiment of the invention, halloysite nanotubes are used as nanoclay particles. The inner lumens of the halloysite nanotubes used in the nanocomposite polymeric material are hollow.
Halloysite is a crystalline clay mineral from the kaolin group, which is available in nature, has a chemical structure of AI2[Si2O5(OH)4].2H2O, and consists of two layers with silica on the outer surface and alumina on the inner surface. The dimensions and shapes of halloysite clay mineral may vary according to the deposit and formation conditions, it may have various morphologies such as tubular, spherical or rod-like, mostly wide tubular form. The halloysite particles used in the nanocomposite polymeric component obtained according to the invention are a natural material exhibiting no toxic effects.
According to another preferred embodiment of the invention, nanocomposite polymeric material is in the form of foam. With the nanocomposite polymeric material being in the foam form, passage of the gas and moisture in the environment is accelerated, thereby ensuring the freshness of the food products such as fresh fruits and vegetables. Moreover, due to the fact that the nanocomposite polymeric material in the form of foam is light-weighted, the use of this material during the storage and transportation of the food products is easier.
In another embodiment of the invention, the nanocomposite polymeric material may be in the form of pad. The use of nanocomposite polymeric material in pad form is very advantageous. In addition to its resistance against physical impacts such as pressure, it is easily and in a very practical manner inserted into the packages where the food products such as fresh fruits and vegetables are stored.
The pores in the nanocomposite polymeric material allow the passage of ethylene gas and moisture through the material. As mentioned, the polymeric material should be porous, so that undesirable gases and moisture can penetrate into the nanocomposite polymeric material and said components are absorbed effectively. In this way, it is observed that undesirable ethylene gas and excess moisture in the environment is significantly reduced. With the use of the porous nanocomposite polymeric material, it is observed that such formations as color change, deterioration, decay, etc. in the food products such as fresh vegetables and fruits are successfully prevented, enabling the food products remain fresh for a long period of time without deterioration in structure.
According to another embodiment of the invention, the foaming agent used for obtaining the nanocomposite polymeric material includes betaine, ammonium stearate, alkanol amide, sodium sulfosuccinate, alkyl-phenol ethoxylate, or a combination thereof. By using said foaming agents, the polymer dispersion is foamed successfully, and it is ensured that the material in the form of a foam or pad retains this structure. In addition, said agents, depending on the hydrophilic groups contained therein, contribute to the moisture retention capability of the resulting nanocomposite polymeric material.
The thickening agent used for obtaining the nanocomposite polymeric material may be cellulosic, alkali-swellable emulsion (ASE), hydrophobically modified alkali-swellable emulsion (HASE) and hydrophobically modified ethoxylated urethane (HEUR), or a combination thereof. With the use of said thickening agents, it is ensured that the polymer dispersion foamed in liquid form still maintains its foam form in liquid form.
The foaming agent used in the nanocomposite polymeric material enables foaming of the polymeric component dispersion while the thickening agent contributes to a more consistent structure thereof. In order to effectively absorb and remove undesirable elements such as ethylene gas and moisture, the nanocomposite polymeric material should be porous and the size of said pores should be large enough to allow the passage of ethylene gas and moisture into the material. When the weight ratio of the foaming agent to thickening agent used herein is in the range of 0.5 - 3.0, preferably 1.0-2.0, it is observed that the diameter of the pores formed in the material ensures maximum ethylene gas and moisture absorption.
In another embodiment of the invention, in the method performed for obtaining the nanocomposite polymeric material, first the dispersion of the polymeric component is prepared. At least one polymeric component is used in the preparation of the polymeric dispersion. Then, a thickening agent and a foaming agent are added to the polymeric component dispersion. Thus, the polymeric component dispersion is foamed. Such addition of the foaming agent and the thickening agent can be performed by any mixing method. Nanoclay particles are added to the foamed dispersion. Once the nanoclay particles are added, they are mixed by any method and dispersed in the polymeric component dispersion. Said mixing method may include mechanical mixing processes. Preferably, high speed mixing method is used.
In another embodiment of the invention, after the polymeric component dispersion is prepared, first the nanoclay particles are added. By subjecting said nanoclay particles to mixing process, the particles are dispersed in the dispersion. The mixing process mentioned herein may be a mechanical mixing method. Thereafter, the polymeric dispersion is foamed by adding the thickening agent and the foaming agent. The mixing processes performed herein can be performed by mechanical methods.
The polymeric component used for obtaining the nanocomposite polymeric material may preferably be polyurethane, polyacrylate, polyester, epoxy, polyvinyl acetate, vinyl polymers, as well as a polymer comprising a group, mixture of copolymers containing at least one of the monomers thereof, or a combination thereof. By selecting polyurethane as the polymeric component, it is observed that the resulting nanocomposite polymeric material is more resistant against physical and environmental conditions.
In the method for obtaining the nanocomposite polymeric material of the invention, a water-based polymer or a molten polymer is suitable to be used as the polymeric component.
According to another embodiment, a water-based polyurethane is used in the method for obtaining the nanocomposite polymeric material.
It is aimed that the nanocomposite polymeric material is used for a long period of time without deterioration in its structure and it is also desired that it is hydrophilic in order to effectively absorb undesirable gases and moisture in the environment.
At this point, in the method of producing the nanocomposite polymeric material, a polyurethane that is obtained by polymerization of diisocyanate monomer, polyol, ionic or hydrophilic chain extender components is suitable to be used, and thus, it is seen that nanocomposite polymeric material having the desired properties is obtained. In addition to the elements mentioned herein, a nonionic or non-hydrophilic chain extender can also be used for obtaining the polyurethane.
According to another embodiment of the invention, the nanoclay particles are dispersed in the polymeric component dispersion. In the method used for obtaining the nanocomposite polymeric material, the average particle diameter of the particles, which are in the form of a water-based dispersion of the polyurethane selected as the polymeric component, is in the range of 50-900 nm, preferably in the range of 50-450 nm.
According to another embodiment of the invention, the polymeric component dispersion in foam form comprising the nanoclay particles is brought into a pad form. This can be performed by known conventional methods. The polymeric component dispersion in foam form comprising the nanoclay particles is in foamed state due to the foaming agent and the thickening agent therein, so the polymeric dispersion is in the foam form. A nanocomposite polymeric material in the form of a pad can be obtained from the foam form by known methods.
In another embodiment of the invention, a nanocomposite polymeric material in the form of a foam can be obtained from the foamed polymeric dispersion by suitable methods.
According to another embodiment of the invention, the nanocomposite polymeric material in foam form is brought into pad form through a separate method step. One of the methods that is suitable to be used is that the nanocomposite polymeric material in form foam can be brought into a pad form by subjecting it to die casting or film casting method.
The nanocomposite polymeric material of the invention is suitable to be used to absorb the ethylene gas and moisture in its environment. With the nanocomposite polymeric material used for preserving the freshness of fresh fruits and vegetables, the ethylene gas and moisture in the environment of the said food products are removed from the environment and neutralized. Thus, said food products can be stored for a long period of time while preserving their freshness.
Food products such as fresh fruits and vegetables are sometimes stored in packages and sometimes in sealed environments such as refrigerators. Therefore, the air in the environment where said food products are placed cannot be replaced as often as necessary, thereby resulting in an increase of undesirable gases such as ethylene gas, as well as formation of moisture in the environment. With the foam form of the nanocomposite polymeric material of the invention, it can be introduced into the environments where food products are stored, in a very practical manner. According to another embodiment of the invention, the nanocomposite polymeric material used to absorb the ethylene gas and capture moisture is in the form of a pad. Thus, it can be introduced into the same environment with the food products during the transportation and storage of the food products, and neutralizes the ethylene gas and moisture in the environment.

Claims

1. A nanocomposite polymeric material comprising at least one polymeric component and nanoclay particles, wherein said material is porous and the material further comprises a thickening agent, a foaming agent, or a combination thereof.
2. A nanocomposite polymeric material according to claim 1, wherein said at least one polymeric component is polyurethane, polyacrylate, polyester, epoxy, polyvinyl acetate, vinyl polymers, a mixture of copolymers containing at least one of a monomer of said polymers, or a combination thereof.
3. A nanocomposite polymeric material according to claim 1 or 2, wherein said polymeric component is a water-based polymer.
4. A nanocomposite polymeric material according to any one of the preceding claims, wherein said polymeric component is polyurethane.
5. A nanocomposite polymeric material according to claim 4, wherein said polymeric component is a water-based polyurethane.
6. A nanocomposite material according to claim 4 or 5, wherein polyurethane is obtained by polymerization of diisocyanate monomer, polyol, ionic or hydrophilic chain extender components.
7. A nanocomposite polymeric material according to claim 6, wherein the amount of polyol in the polyurethane component used for obtaining said nanocomposite polymeric material is in the range of 60-90%, preferably 75-85% by the total weight of the polyurethane.
8. A nanocomposite polymeric material according to any one of claims 4-7, wherein the average particle diameter of the polyurethane particles is in the range of 50-900 nm, preferably 50-450 nm.
9. A nanocomposite polymeric material according to any one of the preceding claims, wherein the weight of said polymeric component is in the range of 35-75% by the total weight of the nanocomposite polymeric material.
10. A nanocomposite polymeric material according to any one of the preceding claims, wherein the total weight of the thickening agent and the foaming agent is in the range of 0.1-15% by the total weight of the nanocomposite polymeric material.
11. A nanocomposite polymeric material according to any one of the preceding claims, wherein the nanoclay particles are dispersed in the polymeric component.
12. A nanocomposite polymeric material according to any one of the preceding claims, wherein the nanoclay particles include halloysite, montmorillonite, sepiolite, cloisite, laponite, or a combination thereof.
13. A nanocomposite polymeric material according to any one of the preceding claims, wherein the weight of the nanoclay particles is in the range of 20-50%, preferably 25- 35%, by the total weight of the nanocomposite polymeric material.
14. A nanocomposite polymeric material according to any one of the preceding claims, wherein the nanoclay particles have a tubular form.
15. A nanocomposite polymeric material according to any one of the preceding claims, wherein hollow halloysite nanotubes are used as nanoclay particles.
16. A nanocomposite polymeric material according to any one of the preceding claims, wherein said nanocomposite polymeric material is in the form a foam.
17. A nanocomposite polymeric material according to any one of the preceding claims, wherein said nanocomposite polymeric material is in the form of a pad.
18. A nanocomposite polymeric material according to any one of the preceding claims, wherein said foaming agent is betaine, ammonium stearate, alkanol amide, sodium sulfosuccinate, alkyl-phenol ethoxylate, or a combination thereof.
19. A nanocomposite polymeric material according to any one of the preceding claims, wherein said thickening agent is a cellulosic, alkali-swellable emulsion, hydrophobically modified alkali-swellable emulsion, and hydrophobically modified ethoxylated urethane, or a combination thereof.
20. A nanocomposite polymeric material according to any one of the preceding claims, wherein the weight ratio of said foaming agent to the thickening agent is in the range of 0.5 - 3.0, preferably 1.0 - 2.0.
21. A method for obtaining a nanocomposite polymeric material according to any one of claims 1-20, comprising the steps of preparing a polymeric dispersion from said at least one polymeric component, foaming said polymeric dispersion by mixing it with the thickening agent and the foaming agent, and then adding nanoclay particles to the foamed dispersion, and mixing.
22. A method according to claim 21, wherein the polymeric component used in the method is a water-based polyurethane.
23. A method according to claim 22, wherein the polyurethane used in the method is obtained by polymerization of diisocyanate monomer, polyol, ionic or hydrophilic chain extender, non-ionic chain extender components.
24. A method according to any one of claims 21-23, wherein the nanoclay particles are dispersed in the polymeric component dispersion.
25. A method according to any one of claims 21 - 24, wherein the nanoclay particles are halloysite, montmorillonite, sepiolite, cloisite, laponite, or a combination thereof.
26. A method according to any one of claims 21-25, comprising the step of forming the polymeric component dispersion in foam a form comprising the nanoclay particles into a pad form.
27. A method according to claim 26, wherein die casting or film casting method is used to die casforming the polymeric component dispersion in foam form into a pad form.
28. Use of a nanocomposite polymeric material according to any one of claims 1-20 for absorbing ethylene gas and moisture in the environment.
29. A use according to claim 28, wherein said nanocomposite polymeric material is used as a material to preserve the freshness of fresh fruits and vegetables.
30. A use according to claim 28 or 29, wherein a nanocomposite polymeric material according to any one of claims 1-20 in the foam form is used.
31. A use according to any one of claims 28-30, wherein a nanocomposite polymeric material according to any one of claims 1-20 in the pad form is used.
PCT/TR2022/051638 2021-12-28 2022-12-27 A polymeric material for preserving the freshness of food products WO2023129067A1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0515764A2 (en) 1991-05-31 1992-12-02 Juan José Fernandez Montreal A method for slowing down the metabolism and controlling the ripening of fruits and similar
WO2005000369A1 (en) 2003-06-30 2005-01-06 World Wide Sales Inc. Absorber composition for ethylene control
WO2007030719A2 (en) * 2005-09-08 2007-03-15 Owens Corning Intellectual Capital, Llc Polystyrene foam containing a modifier-free nanoclay and having improved fire protection performance
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WO2009007715A1 (en) * 2007-07-11 2009-01-15 University Of Strathclyde Fire retardant polyurethane foams
WO2009137539A1 (en) * 2008-05-06 2009-11-12 Huntsman International Llc Clay-isocyanate nanodispersions and polyurethane nanocomposite produced therewith
CN110861381A (en) * 2019-11-21 2020-03-06 上海海洋大学 Antibacterial, shockproof and moisture-absorbing degradable food fresh-keeping pad and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0515764A2 (en) 1991-05-31 1992-12-02 Juan José Fernandez Montreal A method for slowing down the metabolism and controlling the ripening of fruits and similar
WO2005000369A1 (en) 2003-06-30 2005-01-06 World Wide Sales Inc. Absorber composition for ethylene control
US20070227748A1 (en) * 2004-07-02 2007-10-04 John Liggat Fire Retarded Flexible Nanocomposite Polyurethane Foams
WO2007030719A2 (en) * 2005-09-08 2007-03-15 Owens Corning Intellectual Capital, Llc Polystyrene foam containing a modifier-free nanoclay and having improved fire protection performance
WO2009007715A1 (en) * 2007-07-11 2009-01-15 University Of Strathclyde Fire retardant polyurethane foams
WO2009137539A1 (en) * 2008-05-06 2009-11-12 Huntsman International Llc Clay-isocyanate nanodispersions and polyurethane nanocomposite produced therewith
CN110861381A (en) * 2019-11-21 2020-03-06 上海海洋大学 Antibacterial, shockproof and moisture-absorbing degradable food fresh-keeping pad and preparation method thereof

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