WO2019108225A1 - Copolymères et stratifiés comprenant les copolymères - Google Patents

Copolymères et stratifiés comprenant les copolymères Download PDF

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Publication number
WO2019108225A1
WO2019108225A1 PCT/US2017/064197 US2017064197W WO2019108225A1 WO 2019108225 A1 WO2019108225 A1 WO 2019108225A1 US 2017064197 W US2017064197 W US 2017064197W WO 2019108225 A1 WO2019108225 A1 WO 2019108225A1
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WO
WIPO (PCT)
Prior art keywords
copolymer
acid molecules
mixture
fatty acid
groups
Prior art date
Application number
PCT/US2017/064197
Other languages
English (en)
Inventor
William Brenden Carlson
Original Assignee
Xinova, LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xinova, LLC filed Critical Xinova, LLC
Priority to PCT/US2017/064197 priority Critical patent/WO2019108225A1/fr
Publication of WO2019108225A1 publication Critical patent/WO2019108225A1/fr

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Classifications

    • 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
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
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    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
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Definitions

  • Laminates can be designed to protect one or more items (e.g . , food items) that are disposed in an interior of the packaging.
  • Laminates include various layers and at least one of the layers often includes a polymer.
  • polymers that ca be used in the laminates include polyesters, such as polyethylene terephthalate or polylaetic acid.
  • the polymer layer exhibits high oxygen and water permeability which inhibits the laminates ability to protect the one or more items stored within.
  • An example copolymer comprises a plurality of lactic acid groups forming at most about 40 weight % of the copolymer.
  • the copolymer also comprises a plurality of fatty acid groups having about 12 to about 22 carbon atoms.
  • Each of the plurality of fatty acid groups is a derivative of an aliphatic hydroxy-monocarboxylic acid molecule.
  • An example laminate comprises a base layer, at least one additional layer, and a barrier film disposed between the base layer and the at least one additional layer.
  • the barrier film comprises a copolymer.
  • the copolymer comprises a plurality of lactic acid groups and a plurality of fatty 7 acid groups having about 12 to about 22 carbon atoms.
  • the plurality of fatty acid groups are derivatives of a plurality of aliphatic hydroxy- monocarboxylic acid molecules.
  • the barrier film exhibits alower oxygen permeability and a lower water permeability than the base layer or the at least one additional layer.
  • An example method to form a copolymer comprises mixing a plurality 7 of lactic acid molecules with a plurality of fatty acid molecules to form a mixture.
  • Each of the plurality of fatty acid molecul es has about 12 to about 22 carbon atoms and is an aliphatic hydroxy- monocarboxylic acid molecules.
  • the method also comprises polymerizing the mixture to form a copolymer.
  • the copolymer comprises a pl urality of lactic acid groups and a plurality of fatty acid groups. The plurality of lactic acid groups forming at most 40 weight % of the copolymer.
  • An example method to form a laminate comprises providing a base layer and disposing a barrier Him on the base layer
  • Tire barrier film comprises a copolymer.
  • the copolymer comprises a plurality of lactic acid groups and a plurality of fatty acid groups having about 12 to about 22 carbon atoms.
  • the plurality of fatly' acid groups are derivatives of a plurality of aliphatic hydroxy-monocarboxylic acid molecules.
  • the method also comprises placing at least one additional layer on the barrier film.
  • the barrier film exhibits better oxygen permeability and water permeability than the base layer and the at least one additional layer.
  • FIG. 1 is a flow' chart of an example method to form a copolymer
  • FIG. 2 is a schematic cross-sectional view of a copolymer formed according to the method of FIG. 1 ;
  • FIG. 3 is a flow chart of an example method to form a laminate
  • FIG. 4 is a schematic cross-sectional view of a laminate that is formed according to the method of FIG. 3;
  • FIG. 5 is a schematic cross-sectional view' of a package
  • FIG. 6 is a block diagram illustrating an example computing device that is arranged to control any system or device that is configured to perform the method of FIG. 1 or 3;
  • FIG. 7 is a block diagram illustrating an example computer program product that is arranged to store instructions to perform the method of FIGS 1 or 3,
  • An example method of forming the copolymer comprises mixing a plurality of lactic acid molecules with a plurali ty of fatty acid molecules to form a mixture.
  • Each of the plurali ty of fatty acid molecules comprises about 12 to about 22 carbon atoms and is an aliphatic hydroxy-monocarboxylic acid molecule.
  • the method also includes polymerizing the mixture to form a copolymer.
  • the copolymer comprises a plurality of lactic acid groups and a plurality of fatty acid groups.
  • the plurality of lactic acid groups forms at most 40 weight % of the copolymer.
  • the copolymer can form at least a portion of a laminate.
  • FIG. 1 is a flow chart of an example method 100 to form a copolymer, arranged in accordance with at least some of the examples of the present disclosure.
  • the example method 100 may include one or more operations, functions, or actions as illustrated by one or more of blocks 105 or 110.
  • the operations described in the blocks 105 and 1 10 may be performed (or caused to be performed) in response to execution (such as by one or more processors described herein) of computer-executable instructions stored in a tangible and non-transitory computer-readable medium, such as a computer-readable medium of a computing device or some other controller similarly configured.
  • the example method 100 may begin with block 105, which recites“mixing a plurality of lactic acid molecules with a plurality' of fatty' acid molecules to form a mixture.’
  • Block 105 may be followed by block 1 10, which recites“polymerizing the mixture to form a copolymer”
  • the blocks included in the example method 100 are for illustration purposes. In some examples, the blocks may be performed in a different order. In some other examples, various blocks may be eliminated. In still other examples, various blocks may be divided into additional blocks, modified, supplemented with other blocks, or combined into fewer blocks. Other variations of these specific blocks are contemplated, including changes the order of the blocks, changes in the content of the blocks being split or combined into other blocks, etc.
  • the method 100 can include removing the copolymer from a container in which the copolymer was formed
  • Block 105 recites,“mixing a plurality of lactic acid molecules w ith a plurality of fatty acid molecules to form a mixture.”
  • block 105 can include mixing the lactic acid molecules and the fatty acid molecules together in a container, such as a container that the mixture is polymerized.
  • block 105 can include mixing the lactic acid molecules and the fatty acid molecules together using a mechanical mixing device, ultrasonic energy, or another suitable process.
  • block 105 can include mixing the lactic acid molecules and the fatty acid molecules together for a time period (e.g., a few second to more than about 30 minutes) that is sufficient to uniformly mix the lactic acid molecules and the fatty acid molecules together.
  • block 105 can include heating the mixture to a temperature that is sufficient to melt the lactic acid molecules or the fatty acid molecules thereby allowing mixing of the lactic acid molecules and the fatty acid molecules at a molecular level.
  • the mixture includes substantially only the lactic acid molecules and the fatty acid molecules.
  • the mixture can form a blend.
  • the blend can include one or more liquids (e.g., benzene) or one or more additional compounds (e.g., at least one polymerization catalyst).
  • the blend can substantially be free of di carboxylic acid molecules or diols since the dicarboxylic acid molecules and the diols can interfere with the polymerization reaction of block 110.
  • the lactic acid molecules can include lactic acid monomers, lactic acid oligomers, or polylactic acid molecules (e.g., polylactic acid molecules includes more than 10 per units).
  • lactic acid oligomers and, in particular, polylactic acid molecules form a plurality of lactic acid groups (e.g., lactates) that are directly coupled together in the copolymer.
  • the fatty acid groups formed from the fatty acid molecules interact with each other in a manner that causes the copolymer to exhibit good barrier properties (e.g. , low water or oxygen permeation).
  • the plurality of lactic acid groups that are directly coupled together cause the fatty acid groups to be significantly spaced from each other which decreases the barrier properties of the copolymer.
  • the lactic acid molecules can be selected to minimize the number of lactic acid oligomers and, in particular, polylactic acid molecules.
  • the lactic acid monomers can form at least about 50 weight % of the lactic acid molecules, such as at least about 60 weight %, at least about 70 weight %, at least about 80 weight %, at least about 90 weight %, at least about 95 weight %, at least about 99 weight %, or in ranges from about 50 weight % to about 70 weight %, about 60 weight % to about 80 weight %, about 70 weight % to about 90 weight %, about 80 weight % to about 95 weight %, about 90 weight % to about 99 weight %, or about 95 weight % to about 100 weight %.
  • the lactic acid molecules can be at least substantially free of the lactic acid oligomers or, more particularly, at least substantially free of the polylactic acid molecules.
  • the number of carbon atoms in the fatty acid molecules directly affect the barrier properties of the copolymer. For example, most (if not all) of the carbon atoms of a fatty acid molecules forms long carbon atom chains. Generally, the long carbon atom chains remain unaffected during the polymerization reaction of block 1 10. As such, the fatty acid groups of the copolymer includes the same long carbon atom chains as the fatty acid molecules. The carbon atom chains of the copolymer are hydrophobic and interact with each other to form dense layers with limited movement which causes the copolymer to exhibit good barrier properties.
  • the fatty acid molecules can include at least 12 carbon atoms since carbon atom chains that include at least 12 carbon atoms can significantly increase the barrier properties of the copolymer compared to a substantially similar copolymer formed from fatty acid molecules that include less than 12 carbon atoms. Slightly increasing the number of carbon atoms of the fatty acid molecules to be greater than 12 can further improve the barrier properties of the copolymer.
  • fatty acid molecules can include at least 16 carbon atoms can form a copolymer that exhibits barrier properties that are significantly higher than a substantially similar copolymer formed from fatty acid molecules exhibiting less than 16 carbon atoms.
  • the carbon atoms of the fatty acid molecules can include 18 to 22 carbon atoms, such as 18, 20, or 22 carbon atoms.
  • Fatty add molecules that include 18 to 22 carbon atoms form a copolymer that exhibits significantly improved barrier properties compared to a substantially similar copolymer formed from fatty' acid molecules having 16 carbon atoms or less.
  • Increasing the number of carbon atoms of the fatty acid molecules above 22 may only slightly increase, maintain, or decrease the barrier properties of the copolymer compared to substantially similar copolymer that is formed from fatty acid molecules exhibiting 18-22 carbon atoms.
  • increasing the number of carbon atoms of the fatty acid molecules above 22 can adversely affect the elasticity 7 of the copolymer (e.g., the copolymer is brittle), decrease the transparency of the copolymer, significantly increase the difficulty in forming the copolymer (e.g., increase the time required to form the copolymer), etc.
  • the fatty acid molecules include aliphatic hydroxy-monocarboxylic acid molecules.
  • the fatty 7 acid molecules can include a non-branched or non- cyclic aliphatic hydroxy-monocarboxylic acid molecules since branches or cyclic groups can inhibit the formation of the dense layers in the copolymer unless the branches include long carbon chains (e.g., carbon chains including more than 12 carbon atoms).
  • the fatty acid molecules can include saturated fatty acid molecules since unsaturated fatty acid molecules can include long carbon atom chains exhibiting a bent structure. The bent structure of the long carbon atom chains of the unsaturated fatty acid molecules can inhi bit the formation of the dense layers in the copolymer.
  • the fatty acid molecules include aliphatic terminal hydroxy- monocarboxylic acid molecules.
  • a derivative of the aliphatic terminal hydroxyl-monocarboxylic acid molecules comprises a long carbon chain (e.g., 12-22 carbon atom chain) that forms part of the copolymer backbone.
  • the aliphatic terminal hydroxy-monocarboxylic acid molecules can include less than 18 carbon atoms in the long carbon atom chain.
  • the aliphatic terminal hydroxy- monocarboxylic acid molecules can include at least one l2-hydroxy auric acid, 13- hydroxy tridecylic acid, 14-hydroxy myristic acid, 15-hydroxypentadecanoic acid, 16- hydroxy palmitic acid, or I7-hydroxymargaric acid.
  • the aliphatic terminal hydroxy-monocarboxylic acid molecules can include between 18 to 22 carbon atoms.
  • the aliphatic terminal hydroxy-monocarboxylic acid molecules can include 18-hydroxystearic acid, 19-hydroxy nonadecylic acid, 20-hydroxyarachidic acid, 2l-hydroxyheneicosanoic acid, or 22-hydroxybehenic acid.
  • the fatty acid molecules can include 14-hydroxymyristic acid, 16-hydroxypalmitic acid, 18- hydroxystearic acid, 20-hydroxyarachidic acid, or 22-hydroxybehenic acid due to cost.
  • the fatly acid molecules include aliphatic non-terminal hydroxy- monocarboxylic acid molecules.
  • the derivative of the aliphatic non terminal hydroxy -monocarboxylic acid forms long carbon atom side chains (e g., side chains including 12-22 carbon atoms) of the copolymer.
  • the long carbon atom side chains are formed from the long carbon atom chains of the aliphatic non-terminal hydroxy- monocarboxylic acid molecules.
  • the long carbon atom side chains form dense layers that cause the copolymer to exhibit good barrier properties.
  • the aliphatic non terminal hydroxy -monocarboxylic acid molecules can include less than 18 carbon atoms in the long carbon atom side chain.
  • the aliphatic non-terminal hydroxy- monocarboxylic acid molecules can include at least one 2-hydroxyaunc acid, 2- hydroxytridecyiic acid, 2-hydroxymyristic acid, 2-hydroxypentadecanoic acid, 2- hydroxy palmitic acid, or 2-hydroxymargaric acid.
  • the aliphatic non terminal hydroxy -monocarboxylic acid molecules can include between 18 to 22 carbon atoms.
  • the aliphatic non-terminal hydroxy-monocarboxylic acid molecules can include 2-hydroxystearic acid, 2-hydroxynonadecylic acid, 2- hydroxyarachidic acid, 2-hydroxyheneicosanoic acid, or 2-hydroxybehenic acid.
  • the fatty acid molecules can include 2-hydroxymyristic acid, 2-hydroxypalmitic acid, 2-hydroxystearic acid, 2-hydroxyarachidic acid, or 2-hydroxybehenic acid due to cost.
  • the method 100 includes providing preformed fatty acid molecules.
  • block 105 can include mixing the lactic acid molecules with the preformed fatty acid molecules.
  • the method 100 includes making the fatty acid molecules from a plurality of fatty acid molecule precursors (precursors).
  • the method 100 can include making the fatty acid molecules from the precursors before block 105, and then mixing the formed fatty acid molecules with the lactic acid molecules during block 105.
  • block 105 can include making the fatty acid molecules.
  • block 105 can include mixing the lactic acid molecules with the precursors and forming the fatty acid molecules from the precursors concurrently with or after mixing the lactic acid molecules with the precursors.
  • the precursors that form the fatty acid molecules include at least one carboxylic acid having a long carbon atom chain.
  • the at least one carboxylic acid can include one or more of lauric acid, tridecylic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heneicosanoic, or behenic acid.
  • the precursors can form the fatty acid molecules by first contacting the precursors with a halogen-containing compound to form a plurality of terminal halide mono-carboxylic acid molecules.
  • the halogen-containing compound can include bromide, chloride, fluoride, iodide, N-bromosuccinimide, or another suitable halogen-containing compound.
  • Contacting the precursor with the halogen-containing compound can be accompanied with or without applying energy (e.g , ultraviolet light, temperatures greater than room temperature, etc.) to the precursors.
  • energy e.g , ultraviolet light, temperatures greater than room temperature, etc.
  • contacting the precursor with bromide without applying can form the terminal halide mono- carboxylic acid molecules.
  • contacting the precursors with N- bromosuccinimide requires that the precursors be irradiated with ultraviolet light to form the terminal halide mono-carboxylic acid molecules.
  • the terminal halide mono-carboxylic acid molecules can then undergo a hydrolysis reaction to form the fatty acid molecules. For example, contacting the halide mono-carboxylic acid molecules with water or a hydroxide (e.g., sodium hydroxide) can form the fatty acid molecules.
  • a hydroxide e.g., sodium hydroxide
  • the mixture needs to include a substantially equal number of hydroxide groups and carboxylic acid groups (e.g., within 1 molar %) to form the polyester copolymer.
  • Both the lactic acid molecules and the fatty 7 acid molecules disclosed herein include one hydroxide group and one carboxylic group.
  • the mixture includes an equal number of hydroxide groups and carboxylic acid groups regardless of the number of lactic acid molecules or fatty acid molecules that form the mixture in other words, precise control of the amount of lactic acid molecules relative to the fatty 7 acid molecules is not necessary to form the copolymer unlike other polyesters.
  • polyethylene terephthalate is a common polyester. Polyethylene terephthalate is typically formed from terephthalic acid and ethylene glycol.
  • the terephthalic acid includes two carboxylic acid groups and the ethylene glycol includes two hydroxides.
  • precise control of the amount of terephthalic acid relative to ethylene glycol e.g. , the amount of terephthalic acid needs to be the same as the amount of ethylene glycol, ⁇ 1 molar %) to form polyethylene terephthalate.
  • the ability to form the copolymer from any amount of lactic acid molecules relati v e to the fatty acid molecules allows some control over at least some of the properties of the copolymer.
  • the lactic acid molecules and the fatty acid molecules provide different properties to the copolymer and, as such, controlling the amount of lactic acid molecules relative to the fatty acid molecules can be used to select the properties of the copolymer.
  • the fatty acid molecules cause the copolymer to exhibit good barrier properties and the lactic acid molecules cause the copolymer to be biodegradable.
  • Increasing the number of fatty acid molecules relative to the lactic acid molecules can increase the barrier properties and decrease the biodegradabiliiy of the copolymer.
  • increasing the number of lactic acid molecules relative to the fatty acid molecules can increase the biodegradability and decrease the barrier properties of the copolymer.
  • the lactic acid molecules can form at most about 40 weight % of the mixture, such as at most about 35 weight %, at most about 30 weight %, at most about 25 weight %, at most about 20 weight %, at most about 15 weight %, at most about 10 weight %, or at most about 5 weight %.
  • a mixture that includes more than about 40 weight % lactic acid molecules can form a copolymer that exhibiting barrier properties that are too low for certain applications, such as packaging material for food items.
  • the mixture can include at least about 1 weight % lactic acid molecules which causes the copolymer to exhibit acceptable biodegradability.
  • the mixture can include at least about 5 weight % lactic acid molecules (excluding, such at least about 10 weight %, at least about 15 weight %, at least about 20 weight %, or at least about 25 weight %). It is noted that the amount of the lactic acid molecules, in weight %, that are present in the mixture can also depend on other factors. For example, increasing the number of carbon atoms in the fatty acid molecules can decrease the weight % of lactic acid molecules that are present in the mixture.
  • the lactic acid molecules can be present in the mixture in ranges from about 1 weight % to about 10 weight %, about 5 weight % to about 15 weight %, about 10 weight % to about 20 weight %, about 15 weight % to about 25 weight %, about 20 weight % to about 30 weight %, about 25 weight % to about 35 weight %, or about 30 weight % to about 40 weight %.
  • the barrier properties of the copolymer depend on the amount of fatty acid molecules that form the mixture.
  • the fatty acid molecules can form at least 50 molar % of the mixture, such as about 50 molar %, at least about 55 molar %, at least about 60 molar %, at least about 65 molar %, at least about 70 molar %, at least about 75 molar %, at least about 80 molar %, at least about 85 molar %, at least about 90 molar %, at least about 95 molar %, or in ranges from about 50 molar % to about 70 molar %, about 60 molar % to about 80 molar %, about 70 molar % to about 90 molar %, or about 80 molar % to about 98 molar %.
  • a mixture that includes at least about 50 molar % fatty acid molecules can decrease the space between adjacent fatty acid groups thereby increasing the barrier properties of the copolymer.
  • forming the mixture from at least 50 molar % fatly acid molecules causes at least about 25% (e.g., at least about 33% or at least about 50%) of the copolymer to exhibit the structure B-A-B, where B is fatty acid groups and A is lactic acid groups in such an example, the copolymer can be substantially free large sections of lactic acid groups directed bonded together.
  • Block 1 10 recites,‘ ‘ polymerizing the mixture to form a copolymer.”
  • several reactions ca occur.
  • One of the reactions ca include bonding at least some of the lactic acid molecules to at least some of the fatty acid molecules to form lactic acid groups directly bonded to fatty acid groups.
  • Another one of the reactions can include bonding at least some of the lactic acid molecules together to form lactic acid groups directly bonded together.
  • Another one of the reactions ca include bonding at least some of the fatty acid molecules together to form fatly' acid groups directly bonded together.
  • block 110 can include removing a hydroxide from the hydroxide group or carboxylic acid group of a molecule and removing a hydrogen atom from the hydroxide group or carboxylic acid group of another molecule. Removing the hydroxide and hydrogen atoms from the molecules can cause the molecules to bond together. Additionally, the removed hydroxide and hydrogen atoms can combine to form water, hydrogen gas, hydrogen peroxide, or another byproduct.
  • Block 110 can include heating the mixture. Heating the mixture can, at least in part, cause the polymerization reaction or increase the rate of polymerization. Additionally, heating the mixture can cause the lactic acid molecules or fatty acid molecules to melt which can facilitate mixing the mixture or cause uniform polymerization of the mixture.
  • block 110 can include heating the mixture to a temperature that is greater than about 50 °C, greater than about 100 °C, greater than about 150 °C, greater than about 200 °C, about 50 °C to about 125 °C, about 75 °C to about 150 °C, about 100 °C to about 175 °C, about 125 °C to about 200 °C.
  • the temperature that the mixture is heated can be selected based on the melting temperatures of the lactic acid molecules or the fatty acid molecules, whether block 1 10 is performed in the presence of a catalyst, the pressure applied to the mixture, etc.
  • block 110 can include heating the mixture to multiple temperatures.
  • block 1 10 can include heating the mixture to a first temperature and then heating the mixture to a second temperature.
  • Heating the mixture to the first temperature can include heating the mixture to the first temperature over a first time period or holding the mixture at the first temperature for the first time period.
  • heating the mixture to the second temperature can include heating the mixture to the second temperature over a second time period or holding the mixture at the second temperature for the second time period.
  • the multiple temperatures that the mixture is heated to are configured to maintain the mixture below a boiling point thereof
  • the first temperature can be below a boiling point of lactic acid monomers (e.g. , lower than about 122 °C).
  • block 110 can form lactic acid dimers or trimers.
  • the lactic acid dimers or trimers can exhibit a higher boiling temperature than lactic acid monomers.
  • the mixture can be heated to a second temperature that is at, near, or greater than a boiling temperature of lactic acid monomers but less than the boiling temperature of lactic acid dimers or trimers.
  • block 110 can also form lactic acid groups bonded to fatty acid groups which also exhibit a boiling temperature that is greater than lactic acid monomers.
  • block 110 can be performed in an inert atmosphere.
  • block 110 can be performed m a noble gas atmosphere (e.g., an argon atmosphere), a nitrogen atmosphere, a vacuum, or a combination thereof (e.g. , alternating between a noble gas atmosphere and a vacuum).
  • Block 1 10 can be performed in an inert action because oxygen and water can inhibit the polymerization reaction of block 110.
  • block 1 10 can include stirring the mixture during at least a portion of the polymerization reaction. Stirring the mixture during at least a portion of block 110 causes the lactic acid molecules and the fatty acid molecules to remain in an at least substantially homogeneous mixture. The homogeneous mixture substantially prevents a large number of lactic acid groups being directly bonded together. The homogeneous mixture also causes substantially all of the lactic acid molecules and the fatty acid molecules to be polymerized or increase the rate of polymerization.
  • Block 110 can include performing the polymerizing reaction using a reflux technique. The reflux technique allows block 110 to be performed in a liquid (e.g. , organic solvent) substantially without the risk of the liquid evaporating.
  • the mixture of lactic acid molecules and fatly' acid molecules can include or be disposed in the liquid.
  • the liquid can include benzene since benzene, toluene, mesityl ene, xylene, or heptane since such liquids are unlikely to degrade the copolymer or otherwise inhibit the polymerization reaction.
  • block 110 can include adding a catalyst to the mixture that is configured to facilitate the polymerization reaction.
  • block 1 10 can include adding p-toluenesulfonic acid, sulfuric acid, iron trichloride, hathium(IV) chloride tetrahydrofuran complex (1:2), scandium(III) trifluoromethanesulfonate, 1,8- diazabicyclo[5.4.0]undec-7-ene, tetrapropyl titanate, or another suitable catalyst.
  • Block 110 can be performed for a selected time period.
  • the selected time period can be chosen based on a desired molecular weight of the copolymer. For example, increasing the selected tune period can generally increase the molecular weight of the copolymer.
  • block 1 10 can be performed for a selected time period that is sufficient to form a copolymer exhibiting a molecule weight of about 3 kDa to about 90kDa kDa, such as in ranges from about 15 kDa to about 30 kDa, about 25 kDa to about 70 kDa, about 10 kDa to about 25 kDa, about 20 kDa to about 35 kDa, about 30 kDa to about 45 kDa, about 40 kDa to about 55 kDa, about 50 kDa to about 65 kDa, or about 60 kDa to about 70 kDa, about 65 kDa to about 75 kDa, about 70 kDa to
  • the selected time period can be about 0.5 hour to about 8 hour, such as in ranges from about 0.5 hours to about 2 hours, about 1 hour to about 3 hours, about 2 hours to about 4 hours, or about 3 hours to about 5 hours, about 4 hours to about 6 hours, about 5 hours to about 7 hours, or about 6 hours to about 8 hours.
  • block 110 can be performed in a container and, after block 1 10, at least some of the copolymer can adhere to the container.
  • the method 100 can include removing the copolymer from the container. Removing the copolymer from the container can include at least partially dissolving the copolymer in a solvent (e.g., a chloroform solution) to form a solution. The solution can then be removed from the container. The copolymer can be precipitated from the solution by mixing a precipitator (e.g., methanol) with the solution.
  • a precipitator e.g., methanol
  • the method 100 can include drying the copolymer.
  • the copolymer can be disposed in a liquid.
  • the liquid can include benzene, water, the solvent used to remove the copolymer from a container, etc.
  • the liquid can be removed using any suitable method.
  • the copolymer and the liquid can be heated to a boiling temperature of the liquid or disposed in a vacuum.
  • a sponge or another suitable wickmg material can contact the liquid.
  • the method 100 can include forming the copolymer in a barrier film using any suitable method.
  • the method 100 can form the copolymer into a film using an extrusion process (e.g. , blown film extrusion), a pressing process, a molding process (e.g., blo molding), or another suitable process.
  • an extrusion process e.g. , blown film extrusion
  • a pressing process e.g., a pressing process
  • a molding process e.g., blo molding
  • FIG. 2 is a schematic cross-sectional view of a copolymer 200 formed according to the method 100 of FIG. 1, arranged in accordance with at least some of the examples of the present disclosure.
  • the copolymer 200 can form a barrier film.
  • the barrier film can form at least a portion of a laminate.
  • the copolymer 200 includes a plurality of lactic acid groups (e.g., lactate groups) and a plurality' of fatty' acid groups.
  • the fatty' acid groups include about 12 to about 22 carbon atoms and are derivatives of aliphatic hydroxy-monocarboxylic acid molecules (e.g., aliphatic terminal hydroxv-monocarboxylic acid molecules or aliphatic non-terminal hydroxy-monocarboxylic acid molecules).
  • Examples of the fatty' acid groups include laurate, tyridecylate, myristate, pentadecylate, palmitate, margarate, stearate, nonadecyiate, arachidate, or behenate.
  • the copolymer 200 can include poly(lactate-co- !aurate), poly(lactate-co-tyridecylate), poly(lactate-co-myristaie), poly(lactate-co- pentadecylate), poly(laetate-eo-palmitate), poly(lactate-co-margarate), poly(lactate-co- stearate), poly(lactate-co-nonadecylate), poly(lactate-co-arachidate), or polyilactate-co- behenate). It is noted that the weight % and molar % of the lactic acid groups and the fatty acid groups can be the same or substantially similar to the weight and molar % of the lactic acid molecules and fatty acid molecules that formed the copolymer 200.
  • the fatty acid groups of the copolymer 200 form dense layers that are hydrophobic. As such, the fatty acid groups cause the copolymer 200 to exhibit excellent barrier properties.
  • the copolymer 200 exhibits a water permeation that is less than about 0.1 (g/m 2 )/day, such as less than about 0.05 (g/nr)/day, less than about 0.01 (g/m 2 )/day, less than about 0.005 (g/m 2 )/day, less than about 0.001 (g/m 2 )/day, or in ranges from about 0.01 (g/m 2 )/day to about 0.1 (g/m 2 )/day, about 0.005 (g/m 2 )/day to about 0.05 (g/nf)/day, or about 0.001 (g/nr)/day to about 0.01 (g/m 2 )/day.
  • the copolymer 200 exhibits an oxygen permeation that is less than about 1 (cm 3 /m 2 )/day, such as less than about 0.5 (cm 3 /m 2 )/day, less than about 0.1 (cm 3 /m )/day, less than about 0.05 (cm 3 /m 2 )/day, less than about 0.01 (cm 3 /m 2 )/day, or in ranges from about 0.1 (cmr/m 2 )/day to about 1 (cm 3 /m 2 )/day, about 0.05 (cm 3 /m 2 )/day to about 0.5 (crn 3 /m )/day, or about 0.01 (cnf7m )/day to about 0.1 (crn 3 /m )/day It is noted that the barrier properties of the copolymer 200 may depend on the thickness of the copolymer 200.
  • the copolymer 200 can exhibit an yield strength, Young’s modulus, and melting or glass transition temperature that allows the copolymer 200 to form a barrier film, such as a barrier film of a laminate that is used in a packaging material.
  • the copolymer 200 can exhibit a yield strength that is greater than about 1 MPa, such as in ranges from about 1 MPa to about 4 MPa, about 3 MPa to about 6 MPa, about 5 MPa to about 8 MPa, about 7 MPa to about 10 MPa, about 9 MPa to about 12 MPa, about I I MPa to about 14 MPa, or about 4 Pa to about 15 MPa.
  • the copolymer 200 can exhibit a Young’s modulus of about 1 GPa to about 30 GPa, such as in ranges from about 1.5 GPa to about 8.2 GPa, about 1.8 GPa to about 25.6 GPa, about 1 GPa to about 5 GPa, about 2.3 GPa to about 7.5 GPa, about 5 GPa to about 10 GPa, about 7 5 GPa to about 12.5 GPa, about 10 GPa to about 15 GPa, about 12.5 GPa to about 17.5 GPa, about 15 GPa to about 20 GPa, about 17.5 GPa to about 22.5 GPa, about 20 GPa to about 25 GPa, about 22.5 GPa to about 27.5 GPa, or about 25 GPa to about 30 GPa.
  • a Young’s modulus of about 1 GPa to about 30 GPa, such as in ranges from about 1.5 GPa to about 8.2 GPa, about 1.8 GPa to about 2
  • the copolymer 200 can exhibit a melting or glass transition temperature that is greater than about 45 °C, such as in ranges from about 45 °C to about 60 about 55 °C to about 70 °C, about 65 °C to about 80 °C, about 75 °C to about 90 °C, about 85 °C to about 100 °C, about 95 °C to about 1 10 °C, or about 105 °C to about 120 °C.
  • the yield strength, Young’s modulus, or melting or glass transition temperature can depend, at least in part, on the molecular weight of the copolymer 200.
  • the method 100 can include polymerizing the mixture until the copolymer 200 exhibits any of the mechanical properties disclosed herein. It is noted that any of the copolymer molecular weights disclosed herein can be sufficient to cause the copolymer 200 to exhibit any of the mechanical properties disclosed herein.
  • the copolymer 200 can form a barrier film.
  • the barrier film can exhibit a thickness.
  • the barrier film can exhibit a thickness that is less than about 500 pm, less than about 250 pm, less than about 100 pm, less than about 75 pm, less than about 50 pm, less than about 25 pm, less than about 10 pm, less than about 5 pm, or in ranges from about 100 pm to about 500 pm, about 75 pm to about 250 pm, about 50 pm to about 100 pm, about 25 pm to about 75 pm, about 10 pm to about 50 pm, or about 5 pm to about 25 pm.
  • the copolymer 200 can be substantially transparent. In an example, the copolymer 200 can be melt processable. In such an example, the copolymer 200 can form pellets or other bulk structures.
  • the copolymer 200 (e.g., a barrier film of the copolymer 200) can be formed a portion of a laminate that includes two or more layers.
  • the copolymer 200 is susceptible to being degraded when exposed to the atmosphere (e.g., oxygen or water) or being scratched, either of which can adversely affect the barrier properties of the barrier film.
  • the copolymer 200 may not be weldable.
  • the copolymer 200 can form part of a laminate that includes one or more layers that are configured to protect the copolymer 200 from the environment (e.g, an oxygen or water resistant layer), protect the copolymer 200 from scratches (e.g. , an abrasive resistant layer), or to be more weldable than the copolymer 200.
  • FIG. 3 is a flow chart of an example method 300 to form a laminate, arranged in accordance with at least some of the examples of the present disclosure.
  • the example method 300 may include one or more operations, functions or actions as illustrated by one or more of blocks 305, 310, or 315.
  • the operations described in the blocks 305 to 315 may be performed (or caused to be performed) in response to execution (such as by one or more processors described herein) of computer-executable instructions stored in a tangible and non-transitory computer-readable medium, such as a computer-readable medium of a computing device or some other controller similarly configured.
  • the example method 300 may begin with block 305, which recites“providing a base layer.”
  • Block 305 may be followed by block 310, which recites“disposing a barrier film on the base layer, the barrier layer comprising a copolymer.”
  • Block 310 may be followed by block 315, which recites“placing at least one additional layer on the barrier film.”
  • the blocks included in the described the example method 300 are for illustration purposes. In some examples, the blocks may be performed m a different order. In some other examples, various blocks may be eliminated. In still other examples, various blocks may be divided into additional blocks, modified, supplemented with other blocks, or combined together into fewer blocks. Other variations of these specific blocks are contemplated, including changes in the order of the blocks, changes m the content of the blocks being split or combined into other blocks, etc.
  • Block 305 recites,“providing a base layer.”
  • the base layer can be formed from at least one layer, such as a single layer or a plurality of layers (e.g., the base layer is a laminate).
  • the base layer can include at least one paper-based material, at least one cloth, wood, at least one glass, at least one metal film, or at least one polymer.
  • Examples of polymers that can form the base layer includes cellulose, polylactic acid, starch, polyethylene terephthalate, acrylics, polystyrene, another suitable polymer, or combinations thereof.
  • the material of the base layer can be selected to provide one or more characteristics to the laminate, such as one or more properties that the copolymer does not provide.
  • the base layer can exhibit at least one of a water resistance, oxygen resistance, abrasion resistance, or weldability that is greater than the copolymer.
  • the base layer can protect the copolymer or improve the weldability of the laminate.
  • at least a portion of the laminate can be metal free due to the exceptional barrier properties of the barrier film thereby making at least a portion of the packaging material at least partially transparent.
  • Block 310 recites,“disposing a harrier film on the base layer, the barrier layer comprising a copolymer.”
  • the polyamide provided during block 310 is the same as or similar to the copolymer formed in the method 100.
  • block 305 includes providing a preformed copolymer or forming the copolymer according to the method 100 of FIG. 1.
  • block 305 can include providing the barrier layer or forming the copolymer into the barrier layer.
  • Block 310 can include disposing the barrier film on the base layer using any suitable method.
  • block 310 can include coextruding the base layer and the barrier film.
  • block 310 can include disposing the barrier film on the base layer
  • block 310 can include melt processing the base layer and the barrier film.
  • Block 315 recites,“placing at least one additional layer on the barrier film.”
  • the additional layer can be placed on the barrier film using any of the methods disclosed herein (e.g., coextrusion).
  • the additional layer can be formed from any of base layer materials disclosed above.
  • the additional layer can include the same material as or a different material than the base layer.
  • the additional layer can be selected to provide one or more characteristics to the laminate, such as one or more properties that the base layer or the barrier film do not provide. In an example, at least a portion of the additional layer is metal free.
  • FIG. 4 is a schematic cross-sectional view of a laminate 402 that is formed according the method 300 of FIG. 3, arranged in accordance with at least some of the examples of the present disclosure.
  • the laminate 402 includes a barrier film 404 that is the same as, similar to, or formed from the copolymer 200 of FIG. 2.
  • the laminate 402 also includes a base layer 406.
  • the base layer 406 includes at least one layer and is formed from any of the base layer materials disclosed herein.
  • the laminate 402 also includes at least one additional layer 408.
  • the additional layer 408 is formed from any of the base layer materials disclosed herein.
  • the barrier film 404 can be disposed between the base layer 406 and the additional layer 408 such that the base layer 406 and the additional layer 408 can protect the barrier film 404, improve the weldability of the laminate 402, etc.
  • the laminate 402 is substantially free of metals.
  • the portion of the laminate 402 that does not include the metal can be substantially transparent.
  • the laminate 402 exhibits barrier properties that are at least as good as the barrier film 404.
  • the laminate 402 can exhibit a water permeation that is less than about 0.1 (g/nr)/day or an oxygen permeation that is less than about 1 (cm 3 /cm 2 )/day.
  • the barrier film 404 exhibits an oxygen or water permeation that is less than the base layer 406 or the additional layer 408.
  • the base layer 406 can include paper, the bander film 404 includes the copolymer, and the additional layer 408 includes at least one bio-polymer sealant layer.
  • the base layer 406 forms a protection layer (e.g., a polyethylene terephthalate or bi-axia!ly oriented polypropylene layer), the barrier film 404 includes the copolymer, and the additional layer 408 includes a welding layer (e.g, a low density polyethylene or polypropylene layer).
  • the base layer 406 or the additional layer 408 includes polylactic acid and the barrier film 404 includes the copolymer.
  • the base layer 406 or the additional layer 408 can exhibit a first thickness and the barrier film 404 can exhibit a second thickness that is less than the first thickness due to the good barrier properties of the barrier film 404.
  • FIG. 5 is a schemati c cross-sectional view of a package 510, arranged in accordance with at least some of the examples of the present disclosure.
  • the package 510 includes one or more walls 512.
  • the walls 512 can be at least partially formed from any of the copolymers disclosed herein.
  • the walls 512 can be at least partially formed from the copolymer 200 of FIG. 2 that is formed into a barrier film or the laminate 402 of FIG. 4.
  • the walls 512 can form a bag, a cup, a bottle, a film, a plate, a bowl, a box, or another suitable container.
  • the walls 512 at least partially define a chamber 514.
  • the chamber 514 can include or be configured to include at least one item 516 disposed therein.
  • the item 516 can include a food item.
  • the copolymer of the walls 512 can maintain the freshness or increase the shelf-life of the food item.
  • FIG. 6 is a block diagram illustrating an example computing device 600 that is arranged to control any system or device that is configured to perform the method 100 or 300 of FIG. 1 or 3, according to at least one example.
  • computing device 600 typically includes one or more processors 610 and system memory 620.
  • a memory' bus 630 may be used for communicating between the processor 610 and the system memory 620.
  • processor 610 may be of any type including but not limited to a microprocessor (mR), a microcontroller (pC), a digital signal processor (DSP), or any combination thereof.
  • Processor 610 may include one or more levels of caching, such as a level one cache 611 and a level two cache 612, a processor core 613, and registers 614.
  • An example processor core 613 may include an arithmetic logic umt (ALU), a floating point unit (FPU), a digital signal processing core (DSP Core), or any combination thereof.
  • An example memory controller 615 may also be used with the processor 610, or in some implementations, the memory ' controller 615 may be an internal part of the processor 610.
  • system memory 620 may be of any iype including but not limited to volatile memory (such as RAM), non-volatile memor ' (such as ROM, flash memory ⁇ , etc.) or any combination thereof.
  • System memory 620 may include an operating system 621, one or more applications 622, and program data 624.
  • Application 622 may include a control procedure 623 that is arranged to control any of the methods 100 or 300 of FIG. 1 or 3.
  • Program data 624 may include the composition of the fatty' acid molecules, a temperature to heat the mixture of block 105, the time required to perform block 1 10, the composition of the base layer, or other information useful for the operation of the methods 100 or 300.
  • application 622 may be arranged to operate with program data 624 on an operating system 621 such that any of the procedures described herein may be performed.
  • Computing device 600 may have additional features or functionality, and additional interfaces to facilitate communications between the basic configuration 601 and any required devices and interfaces.
  • a bus/interface controller 640 may be used to facilitate communications between the basic configuration 601 and one or more storage devices 650 via a storage interface bus 641.
  • the storage devices 650 may be removable storage devices 651, non-removable storage devices 652, or a combination thereof Examples of removable storage and non-removable storage devices include magnetic disk devices such as flexible disk drives and hard-disk drives (HDDs), optical disk drives such as compact disk (CD) drives or digital versatile disk (DVD) drives, solid state drives (SSDs), and tape drives to name a few.
  • Example computer storage media may include volatile and nonvolatile, removable and non-removable media implemented m any method or technology for storage of information, such as computer readable instructions, data structures, program modules, or other data
  • System memory' 620, removable storage 651 and non-removable storage 652 are all examples of computer storage media.
  • Computer storage media includes, but is not limited to, RAM, ROM, EEPROM, flash memory' or other memory ' technology-, CD-ROM, digital versatile disks (DVD) or other optical storage, magnetic cassettes, magnetic tape, magnetic disk storage or other magnetic storage devices, or any other medium which may be used to store the desired information and which may be accessed by computing device 600. Any such computer storage media may be part of computing device 600.
  • Computing device 600 may also include an interface bus 642 for facilitating communication from various interface devices (e.g., output interfaces, peripheral interfaces, and communication interfaces) to the basic configuration 601 via the bus/interface controller 640.
  • Example output devices 660 include a graphics processing unit 661 and an audio processing unit 662, which may be configured to communicate to various external devices such as a display or speakers via one or more A/V ports 663.
  • Example peripheral interfaces 670 include a serial interface controller 671 or a parallel interface controller 672, which may be configured to communicate with external devices such as input devices (e.g., keyboard, mouse, pen, voice input device, touch input device, etc.) or other peripheral devices (e.g., printer, scanner, etc.) via one or more I/O ports 673.
  • An example computing device 680 includes a network controller 681, which may be arranged to facilitate communications with one or more other computing devices 690 over a network communication link via one or more communication ports 682.
  • the network communication link may be one example of a communication media.
  • Communication media may typically be embodied by computer readable instructions, data structures, program modules, or other data in a modulated data signal, such as a carrier wave or other transport mechanism, and may include any information delivery media.
  • a ‘modulated data signal” may be a signal that has one or more of its characteristics set or changed in such a manner as to encode information in the signal.
  • communication media may include wired media such as a wired netw'ork or direct-wired connection, and wireless media such as acoustic, radio frequency (RF), microwave, infrared (IR) and other wireless media.
  • RF radio frequency
  • IR infrared
  • the term computer readable media as used herein may include both storage media and communication media.
  • Computing device 600 may be implemented as a portion of a small -form factor portable (or mobile) electronic device such as a cell phone, a personal data assistant (PDA), a personal media player device, a wireless web-watch device, a personal headset device, an application specific device, or a hybrid device that include any of the above functions.
  • a small -form factor portable (or mobile) electronic device such as a cell phone, a personal data assistant (PDA), a personal media player device, a wireless web-watch device, a personal headset device, an application specific device, or a hybrid device that include any of the above functions.
  • PDA personal data assistant
  • Computing device 600 may also be implemented as a personal computer including both laptop computer and non-laptop computer configurations.
  • FIG 7 is a block diagram illustrating an example computer program product 700 that is arranged to store instructions to perform the method 100 or 300 of FIGS. 1 or 3, according to at least one example.
  • the signal bearing medium 702 which may be implemented as or include a computer-readable medium 706, a recordable medium 708, a communications medium 710, or combinations thereof, stores programming instructions 704 that may configure the processing unit to perform all or some of the processes previously described. These instructions may include, for example, one or more executable instructions to mix a plurality of lactic acid molecules with a plurality of fatty acid molecules to form a mixture and polymerizing the mixture to form a copolymer.
  • One mole of lactic acid monomers (90.03g) is combined with one mole of 18- hydroxystearic acid (300.27g) to form a mixture.
  • the mixture is disposed in a container that is configured for a reflux.
  • the container includes an inlet coupled to an argon source and an outlet coupled to a vacuum source.
  • the container also includes a mixing device coupled to the container (e.g, a mechanical or magnetic stirring device disposed in the container).
  • the mixing device is configured to mix the lactic acid monomers and the 18- hydroxystearic acid.
  • the container is flushed three times to remove water from the mixture. Each flush includes flowing argon into the container for 3 minutes and then applying a vacuum to the container for 3 minutes.
  • a slow argon flow is provided to the container and the mixture is heated to about 100 °C. Heating the mixture to 100 °C ailowx the lactic acid monomers and the 18-hydroxystearic acid to melt. The mixing device then starts mixing the melted lactic acid monomers and the melted 18-hydroxystearic acid. The mixing device continues to mix the mixture until the viscosity of the mixture increases. Additionally, after melting the lactic acid molecules and the fatty acid molecules, 100 milliliters of benzene is added to the container.
  • the mixture is polymerized by adding p-toluenesulfonic acid to the container and the temperature of the mixture is slowly raised to 130 °C over a two-hour time period, slowly raised to 150 °C over a two hour time period, and then raised to 175 °C over a half hour time period.
  • the mixture is further polymerized by maintaining the temperature of the mixture at 175 °C while stopping the argon flow and decreasing the pressure of the container to 10 mTorr for about 10 minutes and then to a high vacuum for two hours.
  • the resulting copolymer is poly(lactate-co-stearate).
  • the contents of the container e.g. , the copolymer
  • the copolymer is removed from the container by dissolving the copolymer in a 15 weight % solution of chloroform.
  • the solution is then removed from the container.
  • the copolymer is precipitated from the solution by mixing methanol with the solution.
  • the copolymer is then dried (e.g. , the solution is removed from the copolymer) by heating the copolymer to a temperature of about 100 °C.
  • Example 2 is substantially the same as Example 1 except that the copolymer is formed from one mole of 16-hydroxypalmitic acid instead of one mole of 18- hydroxystearic acid. The resulting copolymer is poly(lactate-co-palmitate).
  • Example 2 is substantially the same as Example 1 except that the copolymer is formed from 0.1 moles of lactic acid monomers instead of one mole of lactic acid monomer.
  • the resulting copolymer is poly(laciate-co-stearate).
  • lactic acid monomers 90.03g
  • the container is flushed using the same flushing process as disclosed in Example 1.
  • 100 milliliters of benzene is added to the container.
  • a slow argon flow is then provided to the container and the lactic acid monomers are heated to 100 °C which is sufficient to melt the lactic acid monomers.
  • p-toluenesulfonic acid is added to the container and the container is heated to about 130 °C over a time period of about two hours and to about 150 °C over a time period of about two hours.
  • the container is then allowed to cool to about room temperature. After the container has cooled, one mole of 18-hydroxystearic acid is added to the container. The container is then heated to 100 °C over a two hour time period, then to 130 °C over a two hour time period, and then 150 °C over a two hour time period. The container is then heated to about 175 °C over a half hour time period. While maintaining the container at about 175 °C, the argon flow is stopped and the pressure in the container is reduced to 10 mTorr for 10 minutes and then a high vacuum for 2 hours. The resulting copolymer is polyiiactate- co-stearate).
  • ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. All language such as“up to,”“at least,”“greater than,”“less than,” and the like include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, a range includes each individual member. Thus, for example, a group having 1-3 items refers to groups having 1, 2, or 3 items. Similarly, a group having 1-5 items refers to groups having ! , 2, 3, 4, or 5 items, and so forth.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Ceramic Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)

Abstract

Un exemple selon l'invention de procédé de formation du copolymère comprend le mélange d'une pluralité de molécules d'acide lactique avec une pluralité de molécules d'acide gras pour former un mélange. Chacune de la pluralité de molécules d'acide gras comprend environ 12 à environ 22 atomes de carbone et est une molécule d'acide hydroxymonocarboxylique aliphatique. Le procédé comprend également la polymérisation du mélange pour former un copolymère. Le copolymère comprend une pluralité de groupes acide lactique et une pluralité de groupes acide gras. La pluralité de groupes acide lactique forment au plus 40 % en poids du copolymère. Le copolymère peut former au moins une partie d'un stratifié.
PCT/US2017/064197 2017-12-01 2017-12-01 Copolymères et stratifiés comprenant les copolymères WO2019108225A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0576993A2 (fr) * 1992-06-29 1994-01-05 MITSUI TOATSU CHEMICALS, Inc. Matériau composite dégradable
US5763513A (en) * 1994-05-19 1998-06-09 Mitsui Toatsu Chemicals, Inc. L-lactic acid polymer composition, molded product and film
US5766748A (en) * 1995-11-30 1998-06-16 Mitsui Chemicals, Inc. Stretched film of lactic acid-based polymer
US20030079297A1 (en) * 2001-10-31 2003-05-01 Takemoto Yushi Kabushiki Kaisha Agents and methods for treating biodegradable synthetic yarns
US20040010063A1 (en) * 2001-07-11 2004-01-15 Takayuki Kuroki Aliphatic polyester resin composition and films containing the same
US20060276575A1 (en) * 2005-06-02 2006-12-07 Kao Corporation Plasticizer for biodegradable resin

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0576993A2 (fr) * 1992-06-29 1994-01-05 MITSUI TOATSU CHEMICALS, Inc. Matériau composite dégradable
US5763513A (en) * 1994-05-19 1998-06-09 Mitsui Toatsu Chemicals, Inc. L-lactic acid polymer composition, molded product and film
US5766748A (en) * 1995-11-30 1998-06-16 Mitsui Chemicals, Inc. Stretched film of lactic acid-based polymer
US20040010063A1 (en) * 2001-07-11 2004-01-15 Takayuki Kuroki Aliphatic polyester resin composition and films containing the same
US20030079297A1 (en) * 2001-10-31 2003-05-01 Takemoto Yushi Kabushiki Kaisha Agents and methods for treating biodegradable synthetic yarns
US20060276575A1 (en) * 2005-06-02 2006-12-07 Kao Corporation Plasticizer for biodegradable resin

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