TW201319144A - Degradable six pack rings and compositions and methods relating thereto - Google Patents

Abstract

A container package may include a series of interconnected rings capable of maintaining a plurality of containers in an adjacent relation, at least one ring being formed by a marine-degradable composition comprising at least one polymer that comprises at least one monomer unit selected from the group consisting of succinic acid, 1, 4-butanoic acid, any derivative thereof, and any combination thereof.

Description

Degradable six-package ring, composition and method therefor

The present invention relates to marine degradable compositions and methods therefor, and more particularly, in certain embodiments, to a six-package ring carrier that can degrade in the marine environment.

Because plastics are used to make everyday items such as beverage containers, toys, and furniture, they play an important role in almost every aspect of life. The widespread use of plastics requires proper end-of-life management. Plastics from 1960, when plastics accounted for only one percent of waste streams, increased rapidly to more than 12% of municipal solid waste streams. The largest class of plastics found in containers and packaging (such as soft drink bottles, lids, shampoo bottles), but in durable goods (such as electrical appliances, furniture) and non-durable goods (such as diapers, garbage bags, cups and utensils, These plastics are also found in medical devices.

In 2009, it produced 30 million tons of plastic waste, accounting for 12.3% of the total municipal solid waste. In 2009, the United States produced 13 million tons of containers and packaging plastics. Nearly 11 million tons were durable, and nearly 7 million tons were non-durable. Only 7% of the total amount of plastic waste generated in 2009 was recycled.

Marine litter, especially plastic marine waste, is believed to kill, injure, and cause pain and suffering in wildlife and humans. Plastic marine waste is also believed to cause enormous economic costs and losses for people and communities around the world. Wrapped And swallowing is an example of the dangers that marine debris poses to wildlife. It is also increasingly believed that marine debris is a source of accumulation of toxic substances in the marine environment.

In addition to other requirements, environmentally degradable disposable plastic materials are needed as a possible alternative to a large number of conventional plastic materials that cannot be degraded in the marine environment when discarded. Furthermore, this material should preferably be cost-effective for annual plastic production.

Several degradable polymers have been proposed, including polymers of some hydroxycarboxylic acids such as lactic acid, which are attractive due to their useful physical properties and thermoplasticity. For example, a polymer of a hydroxycarboxylic acid can be degraded into a monomer and a low molecular weight oligomer over time by hydrolysis under general environmental conditions. However, the low temperatures encountered in typical marine environments, due to the extremely slow rate of degradation, make these degradable materials substantially non-degradable.

The present invention relates to marine degradable compositions and methods therefor, and more particularly, in certain embodiments, to a six-package ring carrier that can degrade in the marine environment.

In one embodiment, the container package can comprise a series of interconnected rings that maintain the plurality of containers in an adjacent relationship, wherein at least one of the rings is formed from a marine degradable composition comprising at least one polymer, It comprises at least one monomer unit selected from the group consisting of succinic acid, 1,4-butyric acid, any derivative thereof, and any combination thereof.

In another embodiment, the container package can comprise a series of interconnected rings that maintain the plurality of containers in an adjacent relationship, wherein at least one of the rings is formed from a marine degradable composition comprising at least one polymer It contains poly(butylene succinate).

In another embodiment, a set of packaging containers can comprise a plurality of containers, each container storing a fluid and maintaining an adjacent relationship with another container; and a series of interconnected rings that enable the plurality of containers to maintain an adjacent relationship At least one of the ring systems is formed from a marine degradable composition comprising at least one polymer comprising at least one selected from the group consisting of succinic acid, any derivative thereof, and any combination thereof Body unit.

In another embodiment, a method can include providing a plurality of containers of the same size, placing the containers in a series of interconnected rings, placing each container in a relationship that enables the container to remain adjacent to another container. In one ring, at least one of the rings is formed of a marine degradable composition comprising poly(butylene succinate).

In another embodiment, a method can include providing a marine degradable composition; heating the marine degradable composition to form a polymer melt; and extruding the polymer melt to form a plurality of interconnected rings At least one object composed.

The features and advantages of the present invention will be apparent from the description of the preferred embodiments.

The following illustrations are intended to illustrate specific aspects of the invention and should not be considered as a specific example. Those skilled in the art having the benefit of this disclosure will be able to make a substantial modification and alteration of the subject matter of the present invention and are equivalent in form and function.

The present invention relates to marine degradable compositions and methods therefor, and more particularly, in certain embodiments, to a six-package ring carrier that can degrade in the marine environment.

Many of the advantages of the present invention are that the marine degradable compositions of the present invention provide an inexpensive plastic substitute that is degradable in a non-general environment. This type of plastic is particularly suitable for use in applications where the marine environment may be exposed during the life of the product, and such contact is not the product intended for the intended use. Examples of such products are endless packages (eg for beverages such as soda, beer, water, flavored water and the like); food containers (eg egg cartons, instant food containers and bowls); beverage containers (eg cups) , cans, boxes, bottles); utensils; shopping bags; balloons; fishing lines and fishing nets; hospital supplies (such as bed sheets, surgical gowns, packaging, sample containers, syringes, potty, cotton swabs, hospital curtains and "disposable Use "sterile products"; gloves; bags (such as garbage bags or cleaning bags); diaper pads; packaging materials; toys; buoys; bumpers and retention devices. The methods and compositions of the present invention are particularly suitable for use in non-conventional environments where the temperature drops to less than about 10 ° C at depths greater than about 200 meters, ultraviolet exposure is near zero, and salinity is increased, for example From about 0.05% to about 3% brackish water and from about 3% to about 5% seawater. Should pay attention to the article mentioned The marine degradable composition can be degraded in any marine environment, including but not limited to rivers, streams, caves, lakes, ponds, swamps, marshes, wetlands, intermittent rivers, oceans, seas. , the canal and the like. Marine degradable compositions reduce the risk of entanglement and ingestion with surrounding wildlife in marine environments such as oceans, waterways and beaches.

As used herein, the terms "degradation" and/or "degradable" mean that the material is converted to smaller by hydrolytic degradation, biologically formed entities (eg bacteria or enzymes), chemical reactions, thermal reactions, or radiation-induced reactions. Ingredients, intermediates or final products. The terms "degradation" and/or "degradable" refer to two relatively extreme conditions in which a degradable material may undergo hydrolytic degradation, such as heterogeneous (or overall dissolution) and homogeneous (or surface erosion), and both. Any stage of degradation between. As used herein, the term "marine degradable" and its derivatives refer to degradation and loss of mechanical strength over time, under ambient conditions typically encountered in a salt water or fresh water environment. It should be noted that marine degradation can be carried out via degradation pathways such as chemical hydrolysis, enzymatic hydrolysis, or any combination thereof. At the same time, it should be noted that the marine degradable composition can also be degraded via biodegradation and/or photodegradation, degradation in a non-marine environment, or any combination thereof. Furthermore, marine biodegradable polymers can meet the US Environmental Protection Agency's plastic degradation standards, such as the plastic degradation standards at the priority date of this application. The 40 CFR 238 guidelines outline the degradation criteria for plastic ring carriers (1) AST D-5208-91 after exposure to UV light for 250 hours or (2) during June and July, below latitude 26 Degrees of degradation to 5% elongation at break after exposure to marine conditions in the continental waters of the continental United States, such as the Gulf Coast of Texas and Florida.

The marine degradable compositions of the present invention are considered to be environmentally friendly, not only because they are degradable under unusual environmental conditions, but also because their raw materials can be made from renewable sources, including but not limited to renewable raw materials, like corn. , wheat, cassava, rice, sorghum or lignocellulose, such as corn stover, rice hulls, wheat stalks, wood pulp and the like, and any combination thereof.

In certain embodiments, the marine degradable composition can comprise, consist essentially of, or can comprise a polymer comprising at least a portion of poly(butylene succinate), any derivative thereof, and Any combination thereof. In certain embodiments, the marine degradable composition can comprise, consist essentially of, or can comprise a polymer comprising succinic acid, 1,4-butanediol, any derivative thereof, and At least one monomer unit of any composition.

In certain embodiments, succinic acid can be produced by microbial fermentation of carbohydrates from cereals or starch-containing tubers or hydrolysates from delignified lignocellulosic agricultural waste, followed by separation and purification of the fermentation product. Preferred sources of carbohydrates include corn, sorghum, cassava, tapioca or sweet potato. Preferred agricultural wastes may include corn stover, rice hulls, wheat stalks, and wood pulp. The resulting succinic acid can be used in known industrial processes for the preparation of butanediol (including David Kwana). (Davy-Kvaerner) process or Lurgi-Geminox process) converted to 1,4-butanediol by catalytic hydrogenation.

In certain embodiments, the marine degradable composition can comprise a polymer that is a linear homopolymer or copolymer, a crosslinked homopolymer or copolymer, a block copolymer, an interpolymer, an alternating copolymer, a cycle Copolymers, random polymers, branched homopolymers or copolymers, graft copolymers, star copolymers, brush copolymers, comb copolymers, mixed polymers, and any combination thereof. The term "polymer" as used herein generally refers to homopolymers, copolymers, and hybrid polymers. The term "copolymer" as used herein includes polymers containing two or more monomer species. In certain embodiments, the marine degradable composition can comprise a marine degradable polymer and a marine non-degradable polymer.

In certain embodiments, the marine degradable composition can comprise a copolymer comprising poly(butylene succinate), any derivative thereof, and any combination thereof. Marine degradable and marine non-degradable polymers suitable for forming a copolymer with poly(butylene succinate) may include, but are not limited to, polyurethanes; polyamines; polyureas; polyesters, such as poly (butylene adipate), poly(caprolactone), poly(lactic acid), poly(ε-caprolactone), poly(hydroxybutyrate), poly(hydroxybutyrate-valerate) , poly(hydroxybutyrate-propionate), poly(hydroxybutyrate-hexanoate), poly(hydroxybutyrate-decanoate), poly(hydroxybutyrate-dodecanoate), Poly(hydroxybutyrate-hexadeceate) and poly(hydroxybutyrate-octadecanoate); polyester urethane; aromatic polyester, such as poly (pair) Butylene phthalate), poly(ethylene terephthalate) and poly(trimethylene terephthalate); polyamine; polysaccharide; any derivative thereof; any copolymer thereof; any mixture thereof Polymer; and any combination thereof.

In certain embodiments, the marine degradable composition can comprise a copolymer comprising at least one monomeric unit of succinic acid, any derivative thereof, and any combination thereof. It should be understood that when a polymer comprising a monomer unit is described herein, for the sake of clarity, the monomer unit may refer to an unreacted form rather than a reactive form/polymerized form, and in understanding, the polymer actually comprises Reaction form / polymeric form. Marine degradable and marine non-degradable monomer units suitable for forming copolymers with succinic acid may include, but are not limited to, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, glycols, acid anhydrides, trifunctional monomers, hydroxy acids, hydroxyl groups An acid cyclic diester, an amine, a guanamine, an aniline, any derivative thereof, or any combination thereof. Specific examples of suitable monomer units may include, but are not limited to, lactones; decylamine; dioxanones; lactic acid; glycolic acid; lactide; glycolide; ε-caprolactone; Valerolactone; cyclohexanedicarboxylic acid; terephthalic acid; 1,4-benzenediacetic acid; benzene succinic acid; 2,6-naphthalene dicarboxylic acid; 1,2,3,4,5,6-cyclohexyl Alkane hexacarboxylic acid; 1,2,3,4-cyclopentanetetracarboxylic acid; tetrahydrofuran-2R, 3T, 4T, 5C-tetracarboxylic acid; 1,2,3,4-cyclobutanetetracarboxylic acid; -carboxy-1,1-cyclohexanediacetic acid; 1,3,5-cyclohexanetricarboxylic acid; 1,3,5-trimethyl-1,3,5-cyclohexanetricarboxylic acid; 1α,3α,5β)-1,3,5-trimethyl-1,3,5-cyclohexanetricarboxylic acid; 2,3,4,5-furantetracarboxylic acid; 2-methyl-3, 4,6-pyridine tricarboxylic acid; benzene meta-tricarboxylic acid; pyroic acid; oxalic acid; malonic acid; glutaric acid; adipic acid; pimelic acid; suberic acid; azelaic acid; azelaic acid; Monoalkanoic acid Alkanoic acid; tridecanedioic acid; phthalic anhydride; isophthalic acid; terephthalic acid; undecanedioic acid; dodecanedioic acid, 3,3-dimethylglutaric acid; Alkane-1,2,3,4-tetracarboxylic acid; meso-butane-1,2,3,4-tetracarboxylic acid; 1,3,5-pentanetricarboxylic acid; 2-methylpropane a tricarboxylic acid; 1,2,3-propanetricarboxylic acid; 1,1,2-ethanetricarboxylic acid; 1,2,4-butanetricarboxylic acid; ethylene glycol; diethylene glycol; 3-propanediol; neopentyl glycol; 1,6-hexamethylene glycol; decanediol; 1,4-butanediol; 1,6-hexanediol; 1,4-cyclohexanedimethanol Glycol; bisphenol A; 1,6-hexamethylene diisocyanate; isophorone diisocyanate; methylene diphenyl diisocyanate; toluene diisocyanate; bisphenol diglycidyl ether; glycerol diglycidyl ether; 1,3-cyclohexane bis(methylamine); 1,5-diamino-2-methylpentane; 2,2'-(ethylenedioxy)bis(ethylamine); 2,2- Dimethyl-1,3-propanediamine; 4,4'-(1,1'-biphenyl-4,4'-diyldioxy)diphenylamine; 4,4'-(4,4 '-Isopropyldiphenyl-1,1'-diyldioxy)diphenylamine; 4,4'-diaminobenzimidil; 4,4'-methylene-bis(2- Chloroaniline); 4,4'-Asia Bis(cyclohexylamine); 4,7,10-trioxa-1,13-tridecanediamine; 4,9-dioxa-1,12-dodecanediamine; Aminoethyl)amine; gin(2-aminoethyl)amine; N-(3-aminopropyl)methacrylamide hydrochloride; 2-aminoethyl methacrylate hydrochloride Any derivative thereof; any copolymer thereof; any mixed polymer thereof; and any combination thereof. It should be noted that included in its derivatives are anhydrides of carboxylic acids and polycarboxylic acids. It should be noted that the use of polyfunctional acids and alcohol monomers should be limited so as to limit the possibility of excessive crosslinking, so that the marine degradable composition remains a thermoplastic composition.

In some specific examples, except at least partially comprising a poly In addition to the polymer (butylene succinate), any derivative thereof, and any combination thereof, the marine degradable composition may also contain at least one other polymer. In certain embodiments, the marine degradable composition can comprise at least one other polymer in addition to the polymer comprising at least one monomer unit of succinic acid, any derivative thereof, and any combination thereof. Other suitable polymers include any of the polymers listed herein.

In a non-limiting example, the marine degradable composition can comprise poly(butylene succinate) and poly(butylene succinate) having an average molecular weight of from about 40,000 to about 300,000 and a polydispersity of from about 1.8 to about 4.5. Blend of ester/butylene adipate).

The degradation rate of the marine degradable composition may depend on the type, composition, sequence, length, molecular geometry, molecular weight, stereochemistry, morphology (eg, crystallinity, spherulite size and orientation), hydrophilicity, hydrophobicity, Surface area, additives, and any combination thereof. Furthermore, the environment encountered by degradable surfactants (such as temperature, moisture, oxygen, microorganisms, the presence of enzymes, pH, salinity, light, and the like) may affect how they degrade. Those skilled in the art will benefit from the disclosure, and it should be understood that in selecting the composition and structure of the marine degradable composition, at least some of the factors above may be considered in the composition and possible conditions at which degradation is desired. In a non-limiting example, the weight ratio of poly(butylene succinate) to another marine degradable polymer in the copolymer of the marine degradable composition can range from about 99:1 to about 1:99. Within the scope. Similarly, The weight ratio of the monomer unit of succinic acid and/or 1,4-butanediol to the other marine degradable monomer unit in the copolymer of the marine degradable composition may be from about 99:1 to about 1:99. In the range. The weight ratio of poly(butylene succinate) to marine non-degradable polymer in the copolymer of the marine degradable composition may range from about 99:1 to about 50:50. Similarly, the weight ratio of the succinic acid and/or 1,4-butanediol monomer units to the marine non-degradable monomer units in the copolymer of the marine degradable composition may range from about 99:1 to about 50: Within the range of 50. It should be noted that the upper limit comprising the marine non-degradable polymer and the marine degradable polymer (in the form of a blend and/or copolymer) may be the maximum amount that enables the mechanical strength of the marine degradable composition to reach a desired reduction. Those skilled in the art should be aware that the amount of marine non-degradable polymers and/or marine degradable polymers contained in marine degradable compositions may be different for different marine non-degradable polymers and/or marine degradable polymers. It will be different. Furthermore, in a non-limiting example of polymer unit distribution, a branched copolymer containing a poly(butylene succinate) backbone and a marine non-degradable polymer branch can be compared to poly(butane succinate) The esters are more effectively degraded with linear copolymers of marine non-degradable polymers. Another non-limiting example may be that a block copolymer of poly(butylene succinate) and a marine non-degradable polymer having a degree of polymerization of 10 may degrade more effectively than a degree of polymerization of four.

In certain embodiments, the marine degradable composition can contain an additive. In some embodiments, the additive may include a filler, a plasticizer, an ultraviolet absorber, a light stabilizer, a heat stabilizer, and a lubricant. Agent, antioxidant, degradation promoter, degradation retardant, surface area enhancer, pigment, catalyst for biodegradation-induced photodegradation, processing aid, surface treatment agent, or any combination thereof.

It should be noted that when "about" appears at the beginning of the list of values, "about" is a number that modifies the list of values. It should be noted that some of the lower limits listed may be greater than some of the listed upper limits within the scope of certain numerical lists. Those skilled in the art will appreciate that the selected subset will need to select an upper limit that exceeds the selected lower limit.

Suitable fillers can include, but are not limited to, organic fillers and/or inorganic fillers. Suitable organic fillers may include, but are not limited to, starch; modified starch; cellulose; chitin and chitosan; alginates; proteins such as gluten, zein, casein and collagen; gelatin; Guar gum; xanthan gum; scleroglucan; succinimide; diutan; natural rubber; rosin acid; lignin; natural fiber, such as jute, kenaf, marijuana; Shell; ground wood, such as wood flour; comminuted cellulose, such as pulverized bamboo pulp; any derivative thereof; or any combination thereof. Suitable starch sources can include, but are not limited to, plant sources such as tubers, roots, seeds, fruits, and/or the like of plants. Specific plant sources can include corn, potato, tapioca, rice, wheat, and the like. In certain embodiments, the starch is a combination of pre-gelatinized starch and uncooked starch or native starch. Suitable inorganic fillers may include, but are not limited to, zeolites, silicates, ash, montmorillonite, hydrotalcite, talc, calcium carbonate, glass. Fiber, ceramic powder and ceramic fiber, carbon black, titanium oxide, calcium sulfate and the like, and any combination thereof. It is understood that the filler includes known shapes of all materials, including substantially spherical materials, fibrous materials, polygonal materials (e.g., cubic materials), and combinations thereof. Fillers help to improve stiffness, water permeability and breathability, and dimensional stability, as well as adjust transparency. In some embodiments, the concentration of the filler in the marine degradable composition of the present invention may be at a lower limit of about 0.1%, 1%, 5%, or 10% by weight of the marine degradable composition, to the upper limit of the ocean. The weight of the degrading composition is in the range of about 40%, 30%, 25%, 20%, or 15%, wherein the filler concentration can range from any lower limit to any upper limit and encompass any subset between them.

Suitable plasticizers may include, but are not limited to, di-n-hexyl adipate, bis(2-ethylhexyl) adipate, diisononyl adipate, bis(2-butoxyethyl) adipate. Ester, di-n-hexyl succinate, bis(2-ethylhexyl) succinate, diisononyl succinate, bis(2-butoxyethyl) succinate, bismuthate -ethylhexyl)ester, lactide, ε-caprolactone, glycolide, δ-valerolactone, oligolactic acid, oligolactate, ethyl lactate, ethyl citrate, citric acid Butyl ester, acetonitrile tri-n-butyl citrate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, epoxidized soybean oil, 2-ethylhexyl epoxide, diacetyl phthalate Glycol ester, di(2-ethylbutyrate) triethylene glycol ester, neopentyl glycol ester, alkoxylated sucrose and glucose, sucrose sucrose and glucose, alkylation and deuterated diol, starch ester , N-deuterated amino acid esters, decylamine derivatives and N-deuterated amino acid ester oligomers, polyethylene glycol esters, Tris(2-ethylhexyl) phosphate, dimethyl phthalate, diethyl phthalate, butyl phthalate-2-ethylhexyl phthalate, bis(2-ethyl phthalate) Ethyl ester), dicyclohexyl phthalate, diphenyl phthalate, dimethyl succinate, diethyl succinate, butyl succinate-2-ethylhexyl ester, butyl Bis(2-ethylhexyl) diester, dicyclohexyl succinate, diphenyl succinate, di-n-butyl sebacate and bis(2-ethylhexyl) sebacate, glycerol, Diglycerol and polyglycerol, ethylene glycol or propylene glycol, diethylene glycol and dipropylene glycol, polyethylene glycol, polypropylene glycol, 1,2-propylene glycol, trimethylolethane, trimethylolpropane, neopentyl alcohol , dipentaerythritol, sorbitol, erytritol, xylitol, mannitol, sucrose, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 1,2,6-hexanetriol, 1,3,5-hexane Alcohol, neopentyl glycol and polyvinyl alcohol polymer, polyol acetate, ethoxylate, propoxylate, sorbitol ethoxylate, sorbitol acetate, B Pentaerythritol ester, lactone, indoleamine, dioxanone, lactic acid, glycolic acid, lactide, glycolide, ε-caprolactone, δ-valerolactone, cyclohexanedicarboxylic acid, Terephthalic acid, 1,4-benzenediacetic acid, benzene succinic acid, 2,6-naphthalene dicarboxylic acid, 1,2,3,4,5,6-cyclohexane hexacarboxylic acid, 1,2,3 , 4-cyclopentanetetracarboxylic acid, tetrahydrofuran-2R, 3T, 4T, 5C-tetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 4-carboxy-1,1-cyclohexane Diacetic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,3,5-trimethyl-1,3,5-cyclohexanetricarboxylic acid, (1α, 3α, 5β)-1,3 ,5-trimethyl-1,3,5-cyclohexanetricarboxylic acid, 2,3,4,5-furantetracarboxylic acid, 2-methyl-3,4,6-pyridinetricarboxylic acid, benzene Tricarboxylic acid, pyrophoric acid, grass Acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, o-benzene Dicarboxylic anhydride, isophthalic acid, terephthalic acid, undecanedioic acid, dodecanedioic acid, 3,3-dimethylglutaric acid, butane-1,2,3,4-tetracarboxylate Acid, meso-butane-1,2,3,4-tetracarboxylic acid, 1,3,5-pentanetricarboxylic acid, 2-methylpropanetricarboxylic acid, 1,2,3-propane Carboxylic acid, 1,1,2-ethanetricarboxylic acid, 1,2,4-butanetricarboxylic acid, ethylene glycol, diethylene glycol, 1,3-propanediol, neopentyl glycol, 1,6 -hexamethylene glycol, decanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol triethylene glycol, bisphenol A, 1,6-six Methylene diisocyanate, isophorone diisocyanate, methylene diphenyl diisocyanate, toluene diisocyanate, bisphenol diglycidyl ether, glycerol diglycidyl ether, any derivative thereof, any copolymer thereof, any Mixed polymers, and any combination thereof. It should be noted that included in its derivatives are anhydrides of carboxylic acids and polycarboxylic acids.

In some embodiments, the marine degradable composition can contain a degradable component that, upon degradation, produces a product that can be used to enhance the degradation of the marine degradable composition. In certain embodiments, the degradable component can be an additive, a polymer, a portion of a polymer, a monomer, or any combination thereof. Products useful for degradation can include, but are not limited to, acids. Examples of degradable components that can produce acid upon degradation include, but are not limited to, alpha- or beta-hydroxy acid polyesters, poly(lactic acid), particulate solid anhydrous borate materials, sodium tetraborate, boron oxide, calcium carbonate, magnesium oxide. , and any combination thereof.

In addition to the degrading properties of marine degradable compositions, strength, crystallinity, and processability may be equally important. In a non-limiting example, for a plastic article such as a six-ring carrier, the marine degradable composition should have sufficient strength to maintain carrier integrity during transport and product facing the consumer, with sufficient The degree of crystallinity is such that the container held by the carrier is taken out and has a sufficiently low melting temperature to ensure manufacturability (even directly integrated into current methods). Those skilled in the art, with the benefit of this disclosure, will appreciate that at least the structure and composition of the marine degradable composition can be adjusted to achieve the desired properties.

The appropriate strength of the marine degradable composition can be expressed in terms of Young's modulus, tensile strength, and/or elongation at break. The appropriate Young's modulus of the marine degradable composition, as measured by ASTM D-882, may range from about 0.1 GPa, 0.5 GPa or 1 GPa to an upper limit of about 10 GPa, 7 GPa, 5 GPa or 3 GPa. Where the Young's modulus can range from any lower limit to any upper limit and encompass any subset between them. The appropriate tensile strength of the marine degradable composition, as measured by ASTM D-882, may range from a lower limit of about 10 MPa, 15 MPa or 25 MPa to an upper limit of about 100 MPa, 85 MPa, 75 MPa or 50 MPa, wherein The tensile strength can range from any lower limit to any upper limit and encompass any subset between them. The appropriate elongation at break of the marine degradable composition, as measured by ASTM D-882, may range from about 10%, 50%, 100%, or 250% to the upper limit of about 700%, 500%, or 250. % Within the scope, where the elongation at break can range from any lower limit to any upper limit and encompass any subset between them. The appropriate crystallinity of the marine degradable composition, as measured by ASTM E-793-06, may be at a lower limit of about 0.1%, 1%, 5% or 10% to an upper limit of about 50%, 25%, In the range of 15% or 10%, wherein the degree of crystallinity can range from any lower limit to any upper limit and encompass any subset between them. The appropriate melting temperature of the marine degradable composition, as measured by ASTM E-794-06, may be at a lower limit of about 150 °F, 200 °F, 250 °F or 300 °F to an upper limit of about 450 °F, 400 °F, In the range of 350 °F or 300 °F, where the melting temperature can range from any lower limit to any upper limit and encompass any subset between them.

In some embodiments, the marine degradable compositions of the present invention can be used as a composition of plastic articles such as container wraps (e.g., plastic loop wraps, such as for beverages). In some embodiments, the container package can comprise a series of interconnected rings containing the marine degradable composition of the present invention, non-limiting examples of which are shown in Figures 1A-B, 2, 3 and 4. In some embodiments, a series of interconnected rings can be configured that maintain multiple adjacent items of the same size, i.e., hold a plurality of items of the same size. As used herein, the term "adjacent relationship" includes side-by-side, interlaced, adjacent, circular radial, or any combination thereof. In some embodiments, a series of interconnected rings can include any configured ring including, but not limited to, configuring NxM rings, where N and M can range from about 1 to about 100. In a non-limiting example, a 2x3 configuration is Shown in Figures 1A-B and 2. In some embodiments, the ring can have an inner diameter ranging from about 1/4 inch to about 10 inches.

In some embodiments, the interconnected rings can be a single item. The single article may contain a substantially evenly distributed marine degradable composition of the invention.

In some embodiments, the series of interconnected rings can be attached to the container in a viable manner along any location of the container, including but not limited to neck, cover, top, middle, bottom, or any combination thereof. To keep items (such as containers, fabrics, and articles) in an adjacent relationship. In some embodiments, the rings and articles can have similar cross-sectional shapes. In some embodiments, the article can have a cross-sectional shape that is circular, oval, square, rectangular, polygonal, any hybrid shape thereof, and any combination thereof, including shapes having rounded corners.

In some embodiments, a set of interconnected rings can have any shape. In some embodiments, the articles described above can have any cross-sectional shape and/or can be shape-changeable. Suitable shapes can include, but are not limited to, circles, ovals, squares, rectangles, polygons, any mixed shapes thereof, and any combination thereof (including shapes having rounded corners).

Containers suitable for holding in the series of interconnected rings may be cans, bottles and/or the like, including but not limited to being capable of containing fluids and/or solids, such as beverages (eg, water, milk, soda, beer). , alcoholic beverages, wine, carbonated drinks, juice, flavored water, protein Beverages, nutritious drinks, vitamin fluids, high-calorie fluids, refreshing drinks, sour creamers, flavored drinks and fruit smoothies); foods (eg pickled foods, soups, sauces, nuts, powdered drinks, peanut butter, jelly and Seasonings; paints (eg spray paints); vehicle liquids; household cleaning fluids; medicinal liquids; agricultural products; cans and/or bottles of fertilizers and the like.

Suitable containers may be at least partially composed of poly(butylene succinate), poly(butylene succinate) copolymer, PET, PP, PE, polyolefin, metal, aluminum, cardboard, foil, paper, Or any combination thereof. Fabrics suitable for holding in the series of interconnected loops can be rolled up, folded or the like, including but not limited to articles made of fabric, such as T-shirts, socks, underwear, shorts, pants, swimwear, etc. .

In some embodiments, the series of interconnected rings can be smooth rings or rings having a particular structure, such as the toothed ring shown in FIG.

In some embodiments, the container package can include a series of interconnected rings and a handle that is operable to pick up the series of interconnected rings and suitably hold the container therein. In some embodiments, the handle can be located in the plane of the interconnected rings, parallel to the plane of the interconnected rings, or perpendicular to the plane of the interconnected rings. In some embodiments, the series of interconnected rings and handles can be a single item. The single article may contain a substantially evenly distributed marine degradable composition of the invention. Note The term "handle" as used herein is a generic term that includes hooks, holes, finger holes (as shown in Figures 1A-B and 2), tapes (shown in Figure 3), ribbons, and Perform other configurations of the intended operation.

In some embodiments, the container package can include a series of interconnected rings and features. Suitable features can be integrated with or applied to the container package, and can include, but are not limited to, prints, labels, barcodes, RFID tag punches, and the like, or any combination thereof.

In certain embodiments, the marine degradable compositions of the present invention can be formed into useful articles using a variety of methods known to those skilled in the art including, but not limited to, extrusion, molding, blow molding, coating Fabrication, calendering, lamination, spray, cutting, stamping, die casting, and other methods known in the art. The article can be manufactured in a batch process or in a continuous process (e.g., a commercial continuous process). The article may be made from an intermediate product (e.g., sheet, block, foam, and the like) containing the marine degradable composition of the present invention, and the intermediate product is further processed to form an article. The intermediate product can be made by any known method including, but not limited to, extrusion, molding, coating, calendering, lamination, spraying, and the like, and any combination thereof. It should be noted that the steps of heating the marine degradable composition to form a polymer melt may be included in some of these methods of manufacture. In some embodiments, the article and/or intermediate product can be supplied or shipped to a packaging center or warehouse, and the like.

In some embodiments, the marine degradable composition can be packaged into a container comprising a series of interconnected rings using a number of methods known to those skilled in the art. In some embodiments, the container package can be fabricated from at least one punch and punch module from a substantially planar sheet of the marine degradable composition of the present invention. The method comprises the steps of providing a sheet comprising the marine degradable composition of the present invention and at least one punch and punch module, punching an opening through the sheet, and cutting the container package from the sheet. In other embodiments, a steel ruler cutter can be used to make a container package.

In some embodiments, processing waste (e.g., any cut holes, poorly cut container packages, and the like) can be reprocessed (e.g., remelted) and reshaped into a container package by any known method.

Although the description herein refers at least in part to the application of a container package (e.g., a plastic endless package), those skilled in the art will appreciate the disclosure, and it will be appreciated that the marine degradable compositions of the present invention can be extended to the desired under non-general conditions. Other products that impart some degree of degradability, including but not limited to films; foams; coatings; molded articles, including injection molded articles, blow molded articles, and thermoformed articles; extruded articles, including cast molding or orientation Molding; non-woven fabric; pellets; powder; laminate; adhesive; other packaging materials, such as food containers (such as egg cartons, instant food containers and bowls); beverage containers (such as cups, Cans, outer boxes and bottles); packaging for a wide range of other products; container lids; straws and toothpicks; utensils; shopping bags; hardware; agricultural coverings (eg small bags and mulch for agrochemicals); Fishing line and fishing net; hospital supplies (such as bed sheets, surgical gowns, packaging, sample containers, syringes, potty, cotton swabs, hospital curtains and "single use" sterile products); gloves; safety damage storage packaging; Bag (such as garbage bag or cleaning bag); packaging film; wrapping film; shrinkable film; paper product, card, tape, nozzle cover; fiber; diaper pad; feminine hygiene product Hanger;transport material;packaging material;film box;golf seat;shotgun cartridge;traffic cone;conductive LSI tray;foam bag for AV products and the like;insulation material;toy;garden product;auto parts Coatings, such as those used in cardboard or other containers; products for controlled release of chemicals; and the like.

In some embodiments, the container package can comprise a series of interconnected rings that maintain the plurality of containers in adjacent relationship, wherein at least one of the rings is formed from a marine degradable composition comprising at least one polymer And comprising at least one monomeric unit selected from the group consisting of succinic acid, 1,4-butyric acid, any derivative thereof, and any combination thereof.

In some embodiments, the container package can comprise a series of interconnected rings that maintain the plurality of containers in an adjacent relationship, wherein at least one of the rings is formed from a marine degradable composition, the composition Containing at least one polymer comprising poly(butylene succinate).

In some embodiments, a series of packaging containers can include a plurality of containers, each container storing a fluid and maintaining an adjacent relationship with another container; and a series of interconnected rings that enable the plurality of containers to maintain an adjacent relationship At least one of the ring systems is formed from a marine degradable composition comprising at least one polymer comprising at least one monomer selected from the group consisting of succinic acid, any derivative thereof, and any combination thereof unit.

In some embodiments, a method can include providing a plurality of containers of the same size, placing the containers in a series of interconnected rings, placing each container in a relationship that enables the container to remain adjacent to another container. In one ring, at least one of the rings is formed of a marine degradable composition comprising poly(butylene succinate).

In some embodiments, a method can include providing a marine degradable composition; heating the marine degradable composition to form a polymer melt; and extruding the polymer melt to form a plurality of interconnected rings At least one object composed.

In order to further understand the present invention, the following examples are presented regarding the degradation of poly(butylene succinate). The following examples are not to be construed as limiting or limiting the scope of the invention.

Showa Denko's grade 1001 0.1 mm thick poly(butylene succinate) (PBS) sheet shall have a modulus of approximately 470 MPa (machine direction) and approximately 540 MPa (lateral), approximately 31.1 MPa (machine direction) with a relief strength of about 30.6 (lateral), a breaking strength of about 62.2 MPa (machine direction) and about 59.3 (lateral), and an elongation at break of about 660% (machine direction) and about 710% (lateral). rate. A similar PBS sheet immersed in fresh water should produce a weight loss due to degradation, for example about 50% weight loss after about 90 days (Fig. 5A), corresponding to a loss of tensile strength of about 70%. A similar PBS sheet immersed in salt water should have a weight loss due to degradation, for example about 10% weight loss after about 9 months (Fig. 5B).

A 0.1 mm thick poly(butylene succinate/butylene adipate) (PBSA) sheet impregnated in fresh water should produce a weight loss, for example about 80% weight loss after about 90 days ( Figure 5A). Such PBSA sheets immersed in salt water should cause weight loss due to degradation, for example about 62% weight loss after about 9 months (Fig. 5B).

Thus, the present invention is well adapted to be used in the <RTIgt; The specific embodiments disclosed above are for illustrative purposes only, and the invention may be modified and implemented in a different but equivalent manner. In addition, in addition to the following patent claims In addition to the above, it is not intended to limit the details of the structure or design shown herein. It is therefore evident that the particular embodiments disclosed herein may be modified, combined or modified, and all such variations are within the scope and spirit of the invention. Although the compositions and methods are described in terms of "comprising," "containing," or "comprising" the various components or steps, the compositions and methods may also "consisting essentially" or "consist of" various components and steps. . All values and ranges disclosed above may vary to some extent. Any numerical range falling within the range and any ranges included are specifically disclosed when a numerical range having a lower and upper limit is disclosed. In particular, it should be understood that each numerical range disclosed herein ("from about a to about b" or "approximately from a to b" or the same meaning of "from about ab" Each value and range within a larger range of values. Furthermore, unless the patentee has clearly and clearly defined otherwise, the terms used in the scope of the patent application shall have a literal general meaning. In addition, the indefinite articles "a" or "an", "an" In the event of any conflict with the usage of words or terms in one or more patents or other documents incorporated herein and in the manners that may be cited herein, the definitions consistent with this specification should be used.

1A-B are diagrams showing a non-limiting example of a container package containing a series of interconnected rings.

Figure 2 is a non-limiting example of a container package containing a series of interconnected rings.

Figure 3 is a non-limiting example of a container package containing a series of interconnected rings.

Figure 4 is a non-limiting example of a container package containing a series of interconnected rings.

Figure 5A-B shows the degradation of marine degradable compositions in freshwater and salt water environments.

Claims (30)

A container package comprising: a series of interconnected rings capable of maintaining a plurality of containers in adjacent relationship, wherein at least one ring is formed from a marine degradable composition comprising at least one polymer comprising At least one monomer unit of the group consisting of succinic acid, 1,4-butanediol, any derivative thereof, and any combination thereof. The container package of claim 1, wherein the succinic acid and/or 1,4-butanediol is derived from microbial fermentation. The container package of claim 1, wherein the series of interconnected rings is a single object. The container package of claim 1, wherein the series of interconnected loops are configured with NxM rings, wherein N ranges from about 1 to about 100 and M ranges from about 1 to about 100. The container package of claim 1, wherein the container of the same size has a group selected from the group consisting of a circle, an oval, a square, a rectangle, a polygon, and any mixed shape thereof, including a group having rounded corners, and any combination thereof Cross-sectional shape. Such as the container packaging of claim 1 of the patent scope, wherein the polymerization The substance is selected from the group consisting of linear homopolymers or copolymers, crosslinked homopolymers or copolymers, block copolymers, alternating copolymers, periodic copolymers, random polymers, branched homopolymers or copolymers, grafting At least one of the group consisting of a copolymer, a star copolymer, a brush copolymer, a comb copolymer, a mixed polymer, and any combination thereof. The container package of claim 1, wherein the at least one polymer is a copolymer and further comprises at least one marine degradable second monomer unit, wherein the at least one monomer unit and the at least one second monomer unit The weight ratio is from about 99:1 to about 1:99. The container package of claim 1, wherein the at least one polymer is a copolymer and further comprises at least one marine non-degradable second monomer unit, wherein the at least one monomer unit and the at least one second monomer unit The weight ratio is from about 99:1 to about 50:50. The container package of claim 1, wherein the at least one polymer is a copolymer and further comprises an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, a diol, a trifunctional monomer, a hydroxy acid, or any At least one second monomer unit of the group consisting of derivatives, and any combination thereof. The container package of claim 1, wherein the at least one polymer is a copolymer and further comprises a selected from the group consisting of lactones; indoleamine; dioxanone; lactic acid; glycolic acid; lactide; Glycolide; ε-caprolactone; δ-valerolactone; cyclohexanedicarboxylic acid; terephthalic acid; 1,4-benzenediacetic acid; benzene succinic acid; 2,6-naphthalene dicarboxylic acid; 2,3,4,5,6-cyclohexanehexacarboxylic acid; 1,2,3,4-cyclopentanetetracarboxylic acid; tetrahydrofuran-2R, 3T, 4T, 5C-tetracarboxylic acid; 1,2, 3,4-cyclobutanetetracarboxylic acid; 4-carboxy-1,1-cyclohexanediacetic acid; 1,3,5-cyclohexanetricarboxylic acid; 1,3,5-trimethyl-1, 3,5-cyclohexanetricarboxylic acid; (1α, 3α, 5β)-1,3,5-trimethyl-1,3,5-cyclohexanetricarboxylic acid; 2,3,4,5- Furan tetracarboxylic acid; 2-methyl-3,4,6-pyridinetricarboxylic acid; benzene trimellitic acid; pyroic acid; oxalic acid; malonic acid; glutaric acid; adipic acid; pimelic acid; Diacid; azelaic acid; sebacic acid; undecanedioic acid; dodecanedioic acid; tridecanedioic acid; phthalic anhydride; isophthalic acid; terephthalic acid; undecanedioic acid Dodecanedioic acid, 3,3-dimethylglutaric acid; butane-1,2,3,4-tetracarboxylic acid Meso-butane-1,2,3,4-tetracarboxylic acid; 1,3,5-pentanetricarboxylic acid; 2-methylpropanetricarboxylic acid; 1,2,3-propanetricarboxylic acid ; 1,1,2-ethanetricarboxylic acid; 1,2,4-butanetricarboxylic acid; ethylene glycol; diethylene glycol; 1,3-propanediol; neopentyl glycol; 1,6-six Methylene glycol; decanediol; 1,4-butanediol; 1,6-hexanediol; 1,4-cyclohexanedimethanol triethylene glycol; bisphenol A; 1,6-hexamethylene Diisocyanate; isophorone diisocyanate; methylene diphenyl diisocyanate; toluene diisocyanate; bisphenol diglycidyl Oleic ether; glycerol diglycidyl ether; 1,3-cyclohexane bis(methylamine); 1,5-diamino-2-methylpentane; 2,2'-(ethylenedioxy) double (ethylamine); 2,2-dimethyl-1,3-propanediamine; 4,4'-(1,1'-biphenyl-4,4'-diyldioxy)diphenylamine; , 4'-(4,4'-isopropylidenediphenyl-1,1'-diyldioxy)diphenylamine; 4,4'-diaminobenzimidil; 4,4'-Asia Methyl-bis(2-chloroaniline); 4,4'-methylenebis(cyclohexylamine); 4,7,10-trioxa-1,13-tridecanediamine; 4,9- Dioxa-1,12-dodecanediamine; gin(2-aminoethyl)amine; gin(2-aminoethyl)amine; N-(3-aminopropyl)methacryl An amine hydrochloride; 2-aminoethyl methacrylate hydrochloride; any derivative thereof; and at least one second monomer unit of the group consisting of any combination thereof. The container package of claim 1, wherein the marine degradable composition has a Young's modulus of from about 0.1 GPa to about 10 GPa. The container package of claim 1, wherein the marine degradable composition has a tensile strength of from about 10 MPa to about 100 MPa. The container package of claim 1, wherein the marine degradable composition has an elongation at break of from about 10% to about 700%. The container package of claim 1, wherein the marine degradable composition has a crystallinity of from about 0.1% to about 50%. The container package of claim 1, wherein the marine degradable composition has a melting temperature of from about 150 °F to about 450 °F. The container package of claim 1, wherein the marine degradable composition further comprises a filler selected from the group consisting of a filler, a UV absorber, a light stabilizer, a heat stabilizer, a lubricant, an antioxidant, a degradation promoter, and a degradation retardant. At least one additive comprising a group of surface area enhancers, and any combination thereof. A container package comprising: a series of interconnected rings capable of maintaining a plurality of containers in adjacent relationship, wherein at least one of the rings is formed from a marine degradable composition comprising at least one polymer comprising a poly (butylene succinate). The container package of claim 17 wherein the series of interconnected rings is a single article. For example, the container package of claim 17 of the patent scope, wherein the series of interconnected rings is configured with NxM rings, wherein the range of N From about 1 to about 100 and M ranges from about 1 to about 100. The container package of claim 17 wherein the container of the same size has a shape selected from the group consisting of a circle, an oval, a square, a rectangle, a polygon, and any mixed shape thereof, including a group having rounded corners, and any combination thereof Cross-sectional shape. The container package of claim 17 wherein the polymer is selected from the group consisting of a linear homopolymer or a copolymer, a crosslinked homopolymer or copolymer, a block copolymer, an alternating copolymer, a cyclic copolymer, and a random At least one of the group consisting of a polymer, a branched homopolymer or copolymer, a graft copolymer, a star copolymer, a brush copolymer, a comb copolymer, a mixed polymer, and any combination thereof. The container package of claim 17, wherein the at least one polymer is a copolymer and further comprises a marine degradable polymer, wherein the poly(butylene succinate) and the weight of the marine degradable polymer The ratio is from about 99:1 to about 1:99. The container package of claim 17, wherein the at least one polymer is a copolymer and further comprises a marine non-degradable polymer, wherein the weight of the poly(butylene succinate) and the marine non-degradable polymer The ratio is from about 99:1 to about 50:50. The container package of claim 17 wherein the at least one polymer is a copolymer and further comprises a polyurethane, polyamine, polyurea, polyester, poly(polybutylene adipate) selected from the group consisting of polyurethanes, polyamines, polyureas, polyesters Ester), poly(caprolactone), poly(lactic acid), poly(ε-caprolactone), poly(hydroxybutyrate), poly(hydroxybutyrate-valerate), poly(hydroxybutyrate) -propionate), poly(hydroxybutyrate-hexanoate), poly(hydroxybutyrate-decanoate), poly(hydroxybutyrate-dodecanoate), poly(hydroxybutyrate- Hexadecane ester), poly(hydroxybutyrate-octadecanoate), polyester urethane, aromatic polyester, poly(butylene terephthalate), poly(terephthalic acid) At least one of the group consisting of ethylene glycol ester, poly(trimethylene terephthalate), polyamine, polysaccharide, any derivative thereof, and any combination thereof. The container package of claim 17, wherein the marine degradable composition has a Young's modulus of from about 0.1 GPa to about 10 GPa. The container package of claim 17, wherein the marine degradable composition has a tensile strength of from about 10 MPa to about 100 MPa. The container package of claim 17 wherein the marine degradable composition has an elongation at break of from about 10% to about 700%. The container package of claim 17 wherein the marine degradable composition has a crystallinity of from about 0.1% to about 50%. The container package of claim 17, wherein the marine degradable composition has a melting temperature of from about 150 °F to about 450 °F. The container package of claim 17 , wherein the marine degradable composition further comprises a filler selected from the group consisting of a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a lubricant, an antioxidant, a degradation promoter, and a degradation retardant. At least one additive comprising a group of surface area enhancers, and any combination thereof.