WO2023238149A1 - Composite plastic materials with enhanced barrier properties and novel functionalities - Google Patents

Composite plastic materials with enhanced barrier properties and novel functionalities Download PDF

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Publication number
WO2023238149A1
WO2023238149A1 PCT/IN2023/050528 IN2023050528W WO2023238149A1 WO 2023238149 A1 WO2023238149 A1 WO 2023238149A1 IN 2023050528 W IN2023050528 W IN 2023050528W WO 2023238149 A1 WO2023238149 A1 WO 2023238149A1
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barrier
additive
composition
final
barrier composition
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PCT/IN2023/050528
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French (fr)
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Prerna Goradia
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Prerna Goradia
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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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/04—Esters of silicic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • 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
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the present invention relates to a technical field of preparation of plastic products with barrier properties. More particularly, the invention discloses a composition for providing barrier properties for molded plastics articles and a method thereof.
  • the barrier property of the packaging material is an important criterion while selecting food packaging systems. Barrier properties include permeability of gases (such as 02, CO2, and N2), water vapor, aroma compounds and light and these are vital factors for maintaining the quality of packaged foods. Plastic materials have different degrees of barrier property to gases and liquids. Plastics- based packaging materials provide varying degrees of protection, depending largely on the nature of the polymers used in their manufacture. But since single polymeric film is not able to provide varied protection, multi-layered, laminated, and metallized films are manufactured to meet the varied barrier requirements of food packaging.
  • CN-103289382 relates to a barrier dustproof plastic for an electronic product, and a preparation method thereof.
  • the plastic contains, by mass, 60-75 parts of nylon 6, 3-6 parts of nanometer clay, 10-17 parts of mica, 0.1-0.5 part of a coupling agent, 0.15-0.35 part of an antioxidant 1010, 0.05-0.15 part of an antioxidant 330, 0.4-0.6 part of silane, 5-10 parts of a calcium-zinc stabilizer, 0.4- 1 part of alkyl sodium sulfonate, 0.5-1 part of antimony oxide, 0.3-3 parts of copper chloride, and 0.7-1.5 parts of a dustproof agent.
  • the barrier dustproof plastic has characteristics of good barrier performance, dust resistance, fire retardation and static electricity resistance.
  • US-5958509 relates to a method of coating molded plastics articles which comprises first of all fluorinating, sulfonating, oxidizing or otherwise activating the surface of the articles and then covering them with a silane coating material.
  • a method of coating molded plastics articles which comprises first of all fluorinating, sulfonating, oxidizing or otherwise activating the surface of the articles and then covering them with a silane coating material.
  • CN-106349546 relates to a preparation method of high-barrier and high- density polyethylene (HDPE) plastic, and belongs to the technical field of preparation of plastic products.
  • the preparation method comprises the following steps: mixing and stirring aluminum borate whiskers, attapulgite crystals, isinglass, a sodium hydrogen carbonate solution and talcum powder to obtain a mixture, performing microwave radiation, soaking the mixture into a sulfamic acid solution for heating and dispersion, performing ultrasonic treatment on suspensions, filtering, washing and drying the suspensions on the upper layer, mixing and stirring an obtained material with silicon dioxide, polyisobutylene colloidal particles, stearic acid, organic montmorillonite, HDPE-g-MAH and a silane coupling agent, drying, then adding HDPE plastic powder, performing blending and extrusion through two screw rods to obtain high-barrier HDPE plastic particles, and melting the particles to obtain the high-barrier HDPE plastic.
  • HDPE high-barrier and high- density polyethylene
  • US -20220362999 relates to a synthetic barrier material including a light- cured polymer and graphene nanoplatelets in parallel alignment in the polymer.
  • the graphene nanoplatelets are dispersed in a photocurable resin and polarically aligned by an electric field.
  • a synthetic barrier film manufactured from the aforementioned synthetic barrier material or the aforementioned method.
  • the principle object of the present invention relates to a method and composition to enhance physical barrier properties in plastics and bio-plastics.
  • the present invention attempts to overcome the problems faced in the prior art, and discloses acomposition and method for enhancing the barrier properties and providing novel functionalities to molded plastics articles.
  • the present invention discloses an additive barrier composition for plastics comprising of at least a barrier material compound 0.01-10% (wt/v) comprising of silanes, siloxanes and acrylates for enhancing adhesion and mechanical properties of composites, to provide crosslinking and bind the polymeric materials andat least a delivery particle/excipient 90-99.9 % (wt/v).
  • the barrier compound is preferably with molecular weight > 400 g and very low vapor pressure close to 0.0 ⁇ 1.1 mmHg at 25 °C.
  • the barrier material is at least one selected from a group of reactive silicones comprising tetrakis (2-ethyl hexyl) orthosilicate, tetra butyl orthosilicate, tetra isopropyl orthosilicate and alloys, vinyl functional silicones like vinyl- terminated polydimethylsiloxanes, vinyl methyl siloxane- dimethylsiloxane; Hydride-Functional Silicones like polydimethylsiloxanes, trimethylsiloxy-terminated hydrosiloxanes; Silanol-Functional Silicones like silanol-terminated poly dimethylsiloxanes; Amine-Functional Silicones like amine-terminated polydimethylsiloxanes; Epoxy-Functional Silicones like epoxypropoxypropyl-terminated siloxanes, Acrylates - methacryloxypropyl terminated polydimethylsiloxane and combinations thereof.
  • reactive silicones compris
  • the delivery particle/excipient is selected from a group comprising silica, liquid resins, PET or the molding material itself and combinations thereof.
  • the method for producing an additive barrier composition for composites comprising the steps of (a) mixing at least one or a mixture of barrier compounds elected from a group comprising tetrakis (2-ethyl hexyl) orthosilicate, tetra butyl orthosilicate, tetra isopropyl orthosilicate and combinations thereof with carrier particle in range of 0.01-10% (w/v); (b) grinding the powders from step (a) together into micro fine powder using industrial grinder and ball-milling procedures at high temperatures (up to 700° C); (c) preparing a master batch by a compounding procedure involving mixing of the powder obtained in step (b) with a resin and/or a binder and passing the composition through a twin-screw extruder, wherein the mixture melts in the form of a homogeneous string, followed by cooling and making pellets in turn forming the master batch; and finally mixing the master batch with the compound/article to form the composite with barrier properties.
  • barrier compounds elected from a group
  • the resin/binder is at least one selected from a group comprising silica, liquid resins, PET or the molding material itself and combinations thereof. Further, the proportion of master-batch into the actual resin moulded is 3% to 5% and the proportion of additive into the masterbatch is 3% to 5%.
  • the present invention relates toacomposition and method for enhancing the barrier properties and providing novel functionalities to molded plastics articles.
  • the invention discloses composites developed for food and medical packaging applications, in which certain binding molecules have been used in melt blending and solution casting processing routes to improve the barrier properties to gases and vapors and to impart additional functionalities.
  • the primary inventive step is the addition of specialty binding molecules such as tetraalkoxysilanes which bind to functional groups of the plastics and create mesh like structures and increase the density of the plastic. Tetraalkoxysilanes are mainly used as a crosslinking agent and as precursors to silicon dioxide. Other applications include coatings and in the production of aerogels. These applications exploit the reactivity of the Si-OR bonds.
  • a material with a high barrier property to carbon dioxide may have a very low permeation rate for several gases to permeate through.
  • Polyethylene terephthalate (PET) has been used for soda bottles due to its low carbon dioxide permeation rate.
  • Multilayered containers have been developed to obtain low permeation rates for oxygen, water moisture, fragrance oil, etc.
  • a multilayered film utilizing the different properties of each layer is used in waterproofing applications, such as roofing material and foundation underground waterproofing material.
  • waterproofing applications such as roofing material and foundation underground waterproofing material.
  • the multilayered films typically contain disparate materials which are hard to separate for recycling and therefore expensive.
  • the invention discloses an additive barrier composition for plastics comprising of at least a barrier material compound 0.01- 10% (wt/v) comprising of silanes, siloxanes and acrylates for enhancing adhesion and mechanical properties of composites, to provide crosslinking and bind the polymeric materials andat least a delivery particle/excipient 90-99.9 % (wt/v).
  • the barrier compound is preferably with molecular weight > 400 g and very low vapor pressure close to 0.0 ⁇ 1.1 mmHg at 25 °C.
  • the barrier material silane is at least one selected from a group comprising tetrakis (2-ethyl hexyl) orthosilicate, tetrabutyl orthosilicate, tetraisopropyl orthosilicate and alloys and combinations thereof.
  • the barrier material siloxane is at least one selected from a group of vinylfunctional silicones like vinyl- terminated poly dimethylsiloxanes , vinylmethylsiloxane-dimethylsiloxane ;
  • Hydride-Functional Silicones such as poly dimethylsiloxanes, trimethylsiloxy- terminated hydrosiloxanes; Silanol-Functional Silicones like silanol-terminated poly dimethylsiloxanes; Amine-Functional Silicones like amine-terminated poly dimethylsiloxanes; Epoxy-Functional Silicones like epoxypropoxypropyl- terminated siloxanes and combinations thereof.
  • the barrier material acrylates is at least one selected from methacryloxypropyl terminated polydimethylsiloxane, other acryloxypropyl terminated polydimethyl siloxanes and combinations thereof.
  • the delivery particle/excipient is selected from a group comprising silica, liquid resins, PET or the molding material itself and combinations thereof.
  • the method for producing an additive barrier composition for composites comprising the steps: (a) mixing at least one or a mixture of barrier compounds selected from a group comprising silanes, siloxanes and acrylates and combinations thereof, with a carrier particle in range of 0.01- 10% (w/v) to obtain a powder form; (b) grinding the powders from step (a) together into micro-fine powder using industrial grinder and ball-milling procedures at high temperatures (up to 700° C); (c) preparing a master batch by a compounding procedure involving mixing of the micro-fine powder obtained in step (b) with a resin and/or a binder and passing the composition through a twin- screw extruder, wherein the masterbatch mixture melts in the form of a homogeneous string, followed by cooling and pelletisation in turn forming the final additive barrier composition; and (d) mixing the final additive barrier composition obtained in step (c) with the final compound/article to form the composite with barrier properties.
  • the resin/binder is at least one selected from a group comprising silica, liquid resins, PET or the molding material itself and combinations thereof.
  • the masterbatch getting into actual resin moulded is 1% to 5% of the final additive barrier composition.
  • the pelletisation results in the formation of pellets/granules of the final additive barrier
  • the proportion of additive barrier composition into the final compound/article is 3% to 5% wt/V.
  • the final compound/article is the plastic material, polymer film, textiles, lamination films, medical devices, pharmaceutical packaging, packaging material and combinations thereof to which final additive barrier composition is added for imparting the barrier properties.
  • the masterbatch mixture comprises of grinded and powdered PET 40g, Silica 2g and tetrakis (2-ethyl hexyl) orthosilicate 0.2 g; wherein 1% of this masterbatch is mixed with the resin in turn forming the final additive barrier composition and 5% of this final additive barrier composition is mixed with the compound/article to form the composite with barrier properties.
  • Plastic materials have different degrees of barrier property to gases and liquids.
  • a material with a high barrier property to oxygen may have a very low permeation rate for oxygen to permeate through.
  • Saran has a low oxygen permeation rate and is widely used in food packaging to extend food shelf life.
  • PETE Polyethylene terephthalate
  • Multilayered containers have been developed to obtain low permeation rates for oxygen, water moisture, fragrance oil, etc.
  • Example 1 A method for graphene reinforced polyethylene terephthalate (PET): PET powder was mixed with 2-5% graphene in a grinder process and was then compounded into a master-batch product with 2-5% ratio; and configured the masterbatch product to be suitable for further processing to create a completed product. The product showed superior mechanical properties and some of the results for elongation, stress and strain were noted.
  • PET polyethylene terephthalate
  • Example 2 A method for silica reinforced polyethylene terephthalate (PET): PET powder was mixed with specialty silane molecules with high vapor pressure in 0.1 to 1 % and also ceramic silica powders in 0.1 to 1 % by weight in a grinder process and then compounded it into a master-batch product; and prepared the masterbatch product to be suitable for further processing to create a completed product. Results containing the functional barrier testing using carbon dioxide in PET bottles containing the barrier additive are presented.
  • PET polyethylene terephthalate
  • Example 3 A method for additive reinforced polyethylene terephthalate (PET): a first potion comprising of PET base polymer was mixed with a second portion comprising of a graphene nanoplatelet material that included exfoliated nanoplatelets having an average diameter of 5 micrometers; further a quantity of the second portion was selected to produce a desired percentage by weight of a masterbatch product. The first portion was compounded with the second portion to create the masterbatch product; and the masterbatch product was configured to be suitable for further processing to create a complete product. The product showed superiorCCh retention property and for an additional 12 weeks of shelf life(CC>2 retention) could be maintained.
  • polymer powder, liquid and solid additive elements were mixed to make a powder. Extruded the mix as 5% master-batches in PET resin and added them in the molding process at about 5%. These soft-drink bottles were blow molded and barrier property of the bottle was analyzed.
  • the reason for using the high molecular weight and low vapor pressure molecules is that the PET has a melting point near 270 °C, while the molding temperature is 270 to 280 °C, and hence its injection molding is done at a relatively high temperature and the additives should be stable at those conditions in the mixtures of PET.
  • Other materials such as glass fiber, boron nitride nanoparticles, carbon fibers, and silicon carbide can also be [0043] Advantages:
  • the present invention also encompasses intermediate and end products resulting from the practice of the methods herein.
  • the use of “comprising” or “including” also contemplates embodiments that “consist essentially of’ or “consist of’ the recited feature.
  • embodiments for the present invention have been described in language specific to structural features, it is to be understood that the present invention is not necessarily limited to the specific features described. Rather, the specific features and methods are disclosed as embodiments for the present invention. Numerous modifications and adaptations of the system/component of the present invention will be apparent to those skilled in the art, and thus it is intended by the appended claims to cover all such modifications and adaptations which fall within the scope of the present invention.

Abstract

The present invention relates to a composition for enhancing the barrier properties and providing novel functionalities to molded plastics articles and a method of preparation. The additive materials comprising of PET, silica and silanes for enhancing the adhesion and mechanical properties of composites.

Description

COMPOSITE PLASTIC MATERIALS WITH ENHANCED BARRIER PROPERTIES AND NOVEL FUNCTIONALITIES
FIELD OF THE INVENTION:
[001] The present invention relates to a technical field of preparation of plastic products with barrier properties. More particularly, the invention discloses a composition for providing barrier properties for molded plastics articles and a method thereof.
BACKGROUND OF THE INVENTION
[002] The barrier property of the packaging material is an important criterion while selecting food packaging systems. Barrier properties include permeability of gases (such as 02, CO2, and N2), water vapor, aroma compounds and light and these are vital factors for maintaining the quality of packaged foods. Plastic materials have different degrees of barrier property to gases and liquids. Plastics- based packaging materials provide varying degrees of protection, depending largely on the nature of the polymers used in their manufacture. But since single polymeric film is not able to provide varied protection, multi-layered, laminated, and metallized films are manufactured to meet the varied barrier requirements of food packaging.
[003] References have been made to the following literature:
[004] CN-103289382 relates to a barrier dustproof plastic for an electronic product, and a preparation method thereof. The plastic contains, by mass, 60-75 parts of nylon 6, 3-6 parts of nanometer clay, 10-17 parts of mica, 0.1-0.5 part of a coupling agent, 0.15-0.35 part of an antioxidant 1010, 0.05-0.15 part of an antioxidant 330, 0.4-0.6 part of silane, 5-10 parts of a calcium-zinc stabilizer, 0.4- 1 part of alkyl sodium sulfonate, 0.5-1 part of antimony oxide, 0.3-3 parts of copper chloride, and 0.7-1.5 parts of a dustproof agent. The barrier dustproof plastic has characteristics of good barrier performance, dust resistance, fire retardation and static electricity resistance.
[005] US-5958509 relates to a method of coating molded plastics articles which comprises first of all fluorinating, sulfonating, oxidizing or otherwise activating the surface of the articles and then covering them with a silane coating material. I A method of coating molded plastics articles which comprises first of all fluorinating, sulfonating, oxidizing or otherwise activating the surface of the articles and then covering them with a silane coating material.
[006] CN-106349546 relates to a preparation method of high-barrier and high- density polyethylene (HDPE) plastic, and belongs to the technical field of preparation of plastic products. The preparation method comprises the following steps: mixing and stirring aluminum borate whiskers, attapulgite crystals, isinglass, a sodium hydrogen carbonate solution and talcum powder to obtain a mixture, performing microwave radiation, soaking the mixture into a sulfamic acid solution for heating and dispersion, performing ultrasonic treatment on suspensions, filtering, washing and drying the suspensions on the upper layer, mixing and stirring an obtained material with silicon dioxide, polyisobutylene colloidal particles, stearic acid, organic montmorillonite, HDPE-g-MAH and a silane coupling agent, drying, then adding HDPE plastic powder, performing blending and extrusion through two screw rods to obtain high-barrier HDPE plastic particles, and melting the particles to obtain the high-barrier HDPE plastic.
[007] US -20220362999 relates to a synthetic barrier material including a light- cured polymer and graphene nanoplatelets in parallel alignment in the polymer. The graphene nanoplatelets are dispersed in a photocurable resin and polarically aligned by an electric field. Furthermore, disclosed is a synthetic barrier film manufactured from the aforementioned synthetic barrier material or the aforementioned method. [008] It is evident that despite the presence of wide variety of packaging systems available, it is difficult to obtain all the desirable barrier properties from a single polymeric film. To overcome the problems faced in the prior art, the present invention discloses composite plastic materials with enhanced barrier properties and novel functionalities. The incorporation of additives helps improve general physical properties in plastics and bio-plastics.
[009] The information disclosed in this background of the disclosure section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
OBJECT OF THE INVENTION
[0010] The principle object of the present invention relates to a method and composition to enhance physical barrier properties in plastics and bio-plastics.
SUMMARY OF THE INVENTION:
[0011] The present invention attempts to overcome the problems faced in the prior art, and discloses acomposition and method for enhancing the barrier properties and providing novel functionalities to molded plastics articles.
[0012] In a preferred embodiment the present invention discloses an additive barrier composition for plastics comprising of at least a barrier material compound 0.01-10% (wt/v) comprising of silanes, siloxanes and acrylates for enhancing adhesion and mechanical properties of composites, to provide crosslinking and bind the polymeric materials andat least a delivery particle/excipient 90-99.9 % (wt/v). In an embodiment the barrier compound is preferably with molecular weight > 400 g and very low vapor pressure close to 0.0 ±1.1 mmHg at 25 °C. [0013] In an embodiment the barrier material is at least one selected from a group of reactive silicones comprising tetrakis (2-ethyl hexyl) orthosilicate, tetra butyl orthosilicate, tetra isopropyl orthosilicate and alloys, vinyl functional silicones like vinyl- terminated polydimethylsiloxanes, vinyl methyl siloxane- dimethylsiloxane; Hydride-Functional Silicones like polydimethylsiloxanes, trimethylsiloxy-terminated hydrosiloxanes; Silanol-Functional Silicones like silanol-terminated poly dimethylsiloxanes; Amine-Functional Silicones like amine-terminated polydimethylsiloxanes; Epoxy-Functional Silicones like epoxypropoxypropyl-terminated siloxanes, Acrylates - methacryloxypropyl terminated polydimethylsiloxane and combinations thereof.
[0014] In another embodiment the delivery particle/excipient is selected from a group comprising silica, liquid resins, PET or the molding material itself and combinations thereof.
[0015] In an exemplary embodiment the method for producing an additive barrier composition for composites comprising the steps of (a) mixing at least one or a mixture of barrier compounds elected from a group comprising tetrakis (2-ethyl hexyl) orthosilicate, tetra butyl orthosilicate, tetra isopropyl orthosilicate and combinations thereof with carrier particle in range of 0.01-10% (w/v); (b) grinding the powders from step (a) together into micro fine powder using industrial grinder and ball-milling procedures at high temperatures (up to 700° C); (c) preparing a master batch by a compounding procedure involving mixing of the powder obtained in step (b) with a resin and/or a binder and passing the composition through a twin-screw extruder, wherein the mixture melts in the form of a homogeneous string, followed by cooling and making pellets in turn forming the master batch; and finally mixing the master batch with the compound/article to form the composite with barrier properties.
[0016] In another embodiment the resin/binder is at least one selected from a group comprising silica, liquid resins, PET or the molding material itself and combinations thereof. Further, the proportion of master-batch into the actual resin moulded is 3% to 5% and the proportion of additive into the masterbatch is 3% to 5%.
[0017] The foregoing summary is illustrative only and is not intended to be in any way limiting. In addition to the illustrative aspects, embodiments, and features described above, further aspects, embodiments, and features will become apparent by reference to the drawings and the following detailed description.
DESCRIPTION OF THE PREFERRED EMBODIMENTS:
[0018] While the embodiments of the disclosure are subject to various modifications and alternative forms, specific embodiments thereof have been shown by way of example in the figures and will be described below. It should be understood, however, that it is not intended to limit the disclosure to the particular forms disclosed, but on the contrary, the disclosure is intended to cover all modifications, equivalents, and alternatives falling within the scope of the disclosure. Further, the phraseology and terminology employed in the description is for the purpose of description only and not for the purpose of limitation.
[0019] The terms “comprises”, “comprising”, or any other variations thereof used in the disclosure, are intended to cover a non-exclusive inclusion, such that a device, apparatus, system, assembly, method that comprises a list of components or a series of steps that does not include only those components or steps but may include other components or steps not expressly listed or inherent to such apparatus, or assembly, or device. In other words, one or more elements or steps in a system or device or process proceeded by “comprises. . . a” or “comprising . . .. of’ does not, without more constraints, preclude the existence of other elements or additional elements or additional steps in the system or device or process as the case may be. [0020] The present invention relates toacomposition and method for enhancing the barrier properties and providing novel functionalities to molded plastics articles. In an embodiment, the invention discloses composites developed for food and medical packaging applications, in which certain binding molecules have been used in melt blending and solution casting processing routes to improve the barrier properties to gases and vapors and to impart additional functionalities. The primary inventive step is the addition of specialty binding molecules such as tetraalkoxysilanes which bind to functional groups of the plastics and create mesh like structures and increase the density of the plastic. Tetraalkoxysilanes are mainly used as a crosslinking agent and as precursors to silicon dioxide. Other applications include coatings and in the production of aerogels. These applications exploit the reactivity of the Si-OR bonds. Unlike in the case of mixing of nanoparticles where the materials may be simply embedded in the materials here there are chemical linkages where the bulk material properties are improved due to the bonding network that is formed. The density and overall properties of the material changes which lead to a very superior overall new material with enhanced barrier properties.
[0021] Typically, a material with a high barrier property to carbon dioxide may have a very low permeation rate for several gases to permeate through. Polyethylene terephthalate (PET) has been used for soda bottles due to its low carbon dioxide permeation rate. Multilayered containers have been developed to obtain low permeation rates for oxygen, water moisture, fragrance oil, etc. However, there is a need to further improve the barrier properties for modern applications of food and beverage packaging especially for single layers as they are more recyclable.
[0022] Further a multilayered film utilizing the different properties of each layer is used in waterproofing applications, such as roofing material and foundation underground waterproofing material. There is an opportunity to use the proposed materials of the invention instead of the existing multilayer packaging which is non-recyclable. The multilayered films typically contain disparate materials which are hard to separate for recycling and therefore expensive.
[0023] In a preferred embodiment the invention discloses an additive barrier composition for plastics comprising of at least a barrier material compound 0.01- 10% (wt/v) comprising of silanes, siloxanes and acrylates for enhancing adhesion and mechanical properties of composites, to provide crosslinking and bind the polymeric materials andat least a delivery particle/excipient 90-99.9 % (wt/v). In an embodiment the barrier compound is preferably with molecular weight > 400 g and very low vapor pressure close to 0.0 ±1.1 mmHg at 25 °C.
[0024] In an embodimentof the present invention, the barrier material silane is at least one selected from a group comprising tetrakis (2-ethyl hexyl) orthosilicate, tetrabutyl orthosilicate, tetraisopropyl orthosilicate and alloys and combinations thereof.
[0025] In an embodimentof the present invention, the barrier material siloxane is at least one selected from a group of vinylfunctional silicones like vinyl- terminated poly dimethylsiloxanes , vinylmethylsiloxane-dimethylsiloxane ;
Hydride-Functional Silicones such as poly dimethylsiloxanes, trimethylsiloxy- terminated hydrosiloxanes; Silanol-Functional Silicones like silanol-terminated poly dimethylsiloxanes; Amine-Functional Silicones like amine-terminated poly dimethylsiloxanes; Epoxy-Functional Silicones like epoxypropoxypropyl- terminated siloxanes and combinations thereof.
[0026] In an embodimentof the present invention, the barrier material acrylates is at least one selected from methacryloxypropyl terminated polydimethylsiloxane, other acryloxypropyl terminated polydimethyl siloxanes and combinations thereof.
Figure imgf000008_0001
[0027] In another embodiment the delivery particle/excipient is selected from a group comprising silica, liquid resins, PET or the molding material itself and combinations thereof.
[0028] In an exemplary embodiment the method for producing an additive barrier composition for composites comprising the steps: (a) mixing at least one or a mixture of barrier compounds selected from a group comprising silanes, siloxanes and acrylates and combinations thereof, with a carrier particle in range of 0.01- 10% (w/v) to obtain a powder form; (b) grinding the powders from step (a) together into micro-fine powder using industrial grinder and ball-milling procedures at high temperatures (up to 700° C); (c) preparing a master batch by a compounding procedure involving mixing of the micro-fine powder obtained in step (b) with a resin and/or a binder and passing the composition through a twin- screw extruder, wherein the masterbatch mixture melts in the form of a homogeneous string, followed by cooling and pelletisation in turn forming the final additive barrier composition; and (d) mixing the final additive barrier composition obtained in step (c) with the final compound/article to form the composite with barrier properties.
[0029] In another embodiment of the present invention, the resin/binder is at least one selected from a group comprising silica, liquid resins, PET or the molding material itself and combinations thereof.
[0030] In still another embodiment of the present invention, the masterbatch getting into actual resin moulded is 1% to 5% of the final additive barrier composition.
[0031] In yet another embodiment of the present invention, the pelletisation results in the formation of pellets/granules of the final additive barrier
Figure imgf000009_0001
[0032] In an embodiment of the present invention, the proportion of additive barrier composition into the final compound/article is 3% to 5% wt/V.
[0033] In another embodiment of the present invention, the final compound/article is the plastic material, polymer film, textiles, lamination films, medical devices, pharmaceutical packaging, packaging material and combinations thereof to which final additive barrier composition is added for imparting the barrier properties.
[0034] In an embodiment of the present invention, the masterbatch mixture comprises of grinded and powdered PET 40g, Silica 2g and tetrakis (2-ethyl hexyl) orthosilicate 0.2 g; wherein 1% of this masterbatch is mixed with the resin in turn forming the final additive barrier composition and 5% of this final additive barrier composition is mixed with the compound/article to form the composite with barrier properties.
[0035] Plastic materials have different degrees of barrier property to gases and liquids. A material with a high barrier property to oxygen may have a very low permeation rate for oxygen to permeate through. For example, Saran has a low oxygen permeation rate and is widely used in food packaging to extend food shelf life. Polyethylene terephthalate (PET or PETE) has been used for soda bottles due to its low carbon dioxide permeation rate. Multilayered containers have been developed to obtain low permeation rates for oxygen, water moisture, fragrance oil, etc. Also, multilayered film utilizing the different properties of each layer is used in waterproofing applications, such as roofing material and foundation underground waterproofing material.In an embodiment, graphene is one of the most important materials with extraordinary properties due to the unique atomthick honeycomb-like 2D carbon crystalline structure and in this invention special usage of graphene with respect to its resultant mechanical properties are claimed.
Figure imgf000010_0001
[0036] Example 1. A method for graphene reinforced polyethylene terephthalate (PET): PET powder was mixed with 2-5% graphene in a grinder process and was then compounded into a master-batch product with 2-5% ratio; and configured the masterbatch product to be suitable for further processing to create a completed product. The product showed superior mechanical properties and some of the results for elongation, stress and strain were noted.
[0037] The tensile modulus was measured for the various samples was measured using ASTM D638 and the results are as follows: 1968 MPa (Control), 2165 MPa (silica reinforced PET) and 2323 MPa (Graphene reinforced PET) and a remarkable improvement was seen in this parameter.
[0038] Example 2. A method for silica reinforced polyethylene terephthalate (PET): PET powder was mixed with specialty silane molecules with high vapor pressure in 0.1 to 1 % and also ceramic silica powders in 0.1 to 1 % by weight in a grinder process and then compounded it into a master-batch product; and prepared the masterbatch product to be suitable for further processing to create a completed product. Results containing the functional barrier testing using carbon dioxide in PET bottles containing the barrier additive are presented.
[0039] Example 3: A method for additive reinforced polyethylene terephthalate (PET): a first potion comprising of PET base polymer was mixed with a second portion comprising of a graphene nanoplatelet material that included exfoliated nanoplatelets having an average diameter of 5 micrometers; further a quantity of the second portion was selected to produce a desired percentage by weight of a masterbatch product. The first portion was compounded with the second portion to create the masterbatch product; and the masterbatch product was configured to be suitable for further processing to create a complete product.The product showed superiorCCh retention property and for an additional 12 weeks of shelf life(CC>2 retention) could be maintained.
Figure imgf000011_0001
[0040] In the process, polymer powder, liquid and solid additive elements were mixed to make a powder. Extruded the mix as 5% master-batches in PET resin and added them in the molding process at about 5%. These soft-drink bottles were blow molded and barrier property of the bottle was analyzed.
[0041] The carbonation of the PET bottle was tested with a bi-carbonate salt where 1.4 % of NaHCO3 was mixed with 0.55 % of sulphuric acid and then filled in a bottle where the volume was made up tO 1560 ml. This formulation was designed to mimic actual carbonated drinks bottles.
Results: After 12 months of observation the “barrier” bottles were still tight whereas the control bottles lost the tightness created by the CO2 pressure within 6 weeks.
[0042] The idea is to develop special additives to form composite compounds with the PET so that the end result is a stronger more impervious plastic. Previously known methods involved the formation of coatings etc that can be expensive and non-uniform. Further materials such as graphene with the representative spectral features and also silicates were used to enhance the antimicrobial, barrier and mechanical properties all at once. Specifically, the relatively high molecular weight molecule tetrakis (2-ethyl hexyl) orthosilicate, tetrabutyl orthosilicate, tetraisopropyl orthosilicate preferably with molecular weight > 400 g and very low vapor pressure close to 0.0 ±1.1 mmHg at 25 °C, was used along with small quantities of pure silica. The reason for using the high molecular weight and low vapor pressure molecules is that the PET has a melting point near 270 °C, while the molding temperature is 270 to 280 °C, and hence its injection molding is done at a relatively high temperature and the additives should be stable at those conditions in the mixtures of PET. Other materials such as glass fiber, boron nitride nanoparticles, carbon fibers, and silicon carbide can also be
Figure imgf000012_0001
[0043] Advantages:
• Additives retard microbe growth in finished plastic parts, in turn enhancing product performance
• Helps reduce odor, staining, discoloration and loss of mechanical properties
• Improves barrier properties as seen through functional testing after blow molding of bottles as well as through fundamental gas barrier studies using Mocon (permeation testing analyzers) tools.
• Available for a variety of processes including extrusion, injection molding, blow molding, rotational molding and thermoforming
• Inorganic stable compositions which act as permanent additive in different types of plastics.
[0044] It will be further appreciated that functions or structures of a plurality of components or steps may be combined into a single component or step, or the functions or structures of one-step or component may be split among plural steps or components. The present invention contemplates all of these combinations. Unless stated otherwise, dimensions and geometries of the various structures depicted herein are not intended to be restrictive of the invention, and other dimensions or geometries are possible. In addition, while a feature of the present invention may have been described in the context of only one of the illustrated embodiments, such feature may be combined with one or more other features of other embodiments, for any given application. It will also be appreciated from the above that the fabrication of the unique structures herein and the operation thereof also constitute methods in accordance with the present invention. The present invention also encompasses intermediate and end products resulting from the practice of the methods herein. The use of “comprising” or “including” also contemplates embodiments that “consist essentially of’ or “consist of’ the recited feature. [0045] Although embodiments for the present invention have been described in language specific to structural features, it is to be understood that the present invention is not necessarily limited to the specific features described. Rather, the specific features and methods are disclosed as embodiments for the present invention. Numerous modifications and adaptations of the system/component of the present invention will be apparent to those skilled in the art, and thus it is intended by the appended claims to cover all such modifications and adaptations which fall within the scope of the present invention.

Claims

CLAIMS,
1. An additive barrier composition for plastics comprising: at least a barrier material compound 0.01-10% (wt/v); wherein the barrier compound preferably has molecular weight > 400 g and vapor pressure close to 0.0 ±1.1 mmHg at 25 °C; and at least a delivery particle/ excipient 90-99.9 % (wt/v).
2. The additive composition as claimed in claim 1, wherein the barrier material is at least one selected from a group of silanes, siloxanes and acrylates.
3. The additive composition as claimed in claim 2, wherein the barrier material silane is at least one selected from a group comprising tetrakis (2-ethyl hexyl) orthosilicate, tetrabutyl orthosilicate, tetraisopropyl orthosilicate and combinations thereof.
4. The additive composition as claimed in claim 2, wherein the barrier material siloxane is at least one selected from a group of vinylfunctionalsilicones such as vinyl-terminated poly dimethylsiloxanes , vinylmethylsiloxane-dimethylsiloxane ;
Hydride-Functional Silicones such as poly dimethylsiloxanes, trimethylsiloxy-terminated hydrosiloxanes; Silanol-Functional
Silicones like silanol-terminated polydimethylsiloxanes; Amine- Functional Silicones like amine-terminated poly dimethylsiloxanes; Epoxy-Functional Silicones such as epoxypropoxypropyl-terminated siloxanes and combinations thereof.
5. The additive composition as claimed in claim 2, wherein the barrier material acrylatesis at least oneselected from methacryloxypropylterminated polydimethylsiloxane, other acryloxypropyl terminated polydimethylsiloxanesand combinations thereof. The additive composition as claimed in claim 1, wherein the delivery particle/excipient is selected from a group comprising silica, liquid resins, PET or the molding material itself and combinations thereof. A method for producing an additive barrier composition for composites comprising the steps: a. mixing at least one or a mixture of barrier compounds selected from a group comprising silanes, siloxanes and acrylates and combinations thereof, with a carrier particle in range of 0.01-10% (w/v) to obtain a powder form; b. grinding the powders from step (a) together into micro-fine powder using industrial grinder and ball-milling procedures at high temperatures (up to 700° C); c. preparing a master batch by a compounding procedure involving mixing of the micro-fine powder obtained in step (b) with a resin and/or a binder and passing the composition through a twin-screw extruder, wherein the masterbatch mixture melts in the form of a homogeneous string, followed by cooling and pelletisation in turn forming the final additive barrier composition; and d. mixing the final additive barrier composition obtained in step (c) with the final compound/article to form the composite with barrier properties. The method for producing additive barrier composition for composites as claimed in claim 7, wherein the resin/binder is at least one selected from a group comprising silica, liquid resins, PET or the molding material itself and combinations thereof. The method for producing additive barrier composition for composites as claimed in claim 7, wherein the masterbatch getting into actual resin moulded is 1 % to 5 % of the final additive barrier composition. The method for producing additive barrier composition for composites as claimed in claim 7, wherein the pelletisation results in the formation of pellets/ granules of the final additive barrier composition. The method for producing additive barrier composition for composites as claimed in claim 10, wherein proportion of additive barrier composition into the final compound/article is 3% to 5% wt/V. The method for producing additive barrier composition for composites as claimed in claim 11, wherein the final compound/ article is the plastic material, polymer film, textiles, lamination films, medical devices, pharmaceutical packaging, packaging material and combinations thereof to which final additive barrier composition is added for imparting the barrier properties. The method for producing the additive barrier composition for composites as claimed in claim 7, wherein the master batch mixture comprises of grinded and powdered PET 40 g, Silica 2 g and tetrakis (2-ethyl hexyl) orthosilicate 0.2 g; wherein 1% of this masterbatch is mixed with the resin in turn forming the final additive barrier composition and 5% of this final additive barrier composition is mixed with the compound/article to form the composite with barrier properties.
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* Cited by examiner, † Cited by third party
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US20200362137A1 (en) * 2018-01-16 2020-11-19 Rutgers, The State University Of New Jersey Use of graphene-polymer composites to improve barrier resistance of polymers to liquid and gas permeants

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