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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/24—Catalysts containing metal compounds of tin
  • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
  • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
  • C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
  • C08G18/463—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing nitro groups
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/757—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the cycloaliphatic ring by means of an aliphatic group
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
  • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7678—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing condensed aromatic rings
• • 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
  • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
  • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
  • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/6856—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/053—Polyhydroxylic alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
  • C08K5/134—Phenols containing ester groups
  • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
  • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
  • C08K5/24—Derivatives of hydrazine
• • C—CHEMISTRY; METALLURGY
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3472—Five-membered rings
  • C08K5/3475—Five-membered rings condensed with carbocyclic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
  • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
• • 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
  • C08G2110/00—Foam properties
  • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

• thermoplastic polyurethane (TPU) compositions comprising polyesters containing dicarboxylic acids and nitro- substituted dicarboxylic acids from recycled feedstocks.
• TPU elastomers are used in a variety of applications such as footwear, automotive parts, tubes, hoses, as well as other applications.
• TPU elastomers are typically the reaction product of one or more diisocyanate compounds, one or more high equivalent weight diols (polyester or polyether), and one or more chain extenders.
• the high equivalent weight diol of choice is a polyester diol, such as adipate polyester or polycaprolactone.
• Cast elastomers prepared from polyester diols in general have better mechanical properties than elastomers prepared from polyether diols.
• the polyester diols impart desirable mechanical properties and abrasion resistance to the TPU which makes the TPU elastomer useful in footwear applications.
• TPUs are expanding into novel application spaces such as 3D printing. Such applications require high hardness and tensile strength while retaining the desired flexibility of TPU elastomers.
• U.S. Patent No. 5,844,165 discloses nitromalonate polyesters that are useful in high energy propellants.
• preferred nitromalonate polyesters contain R 1 and R 2 groups that are both -CH2ONO2.
• the preferred nitromalonate s described by this ’ 165 patent are substituted by two nitro-methane groups between the two carboxy groups of the malonate, providing an energetic composition.
• U.S. Patent No. 3,745,076 discloses the reaction product of 4,4-dinitropimelic acid and diethylene glycol that results in a polester polyol containing hydroxy groups that can be reacted with polyisocyanates.
• the nitro is the substituent group
• the multiple nitro groups are preferred, as it is an object of this ’076 patent to produce a binder having a higher total energy content.
• Nitro-functionalized diacids are the product of chemically recycled polyethylene via Accelerated Thermal Oxidative Decomposition (ATODTM). These diacids can be used to synthesize nitro-functionalized polyester diols which are a major building block for thermoplastic polyurethanes. These nitro-functionalized polyester diols are the first polyols synthesized from monomers derived from chemically recycled post-consumer polyethylene.
• TPU elastomer from a polyester diol that is economical, is made from recycled content, and exhibits excellent mechanical properties.
• This invention provides a TPU elastomer which is a polymer of (1) at least one high equivalent weight polyester diol containing nitro functionality on the backbone derived from mixtures of dicarboxylic acids and nitro-dicarboxylic acids as well as a polyesterdiol not containing any nitro groups, (2) at least one chain extender and (3) at least one diisocyanate.
• polyesterdiol not containing any nitro groups provides a non-energenic TPU useful for consumer goods.
• TPU elastomer which is a polymer of (1)
• nitro-functionalized polyester diol made from a mixture of dicarboxylic acids, nitro-dicarboxylic acids, and 1,4-butanediol, or a mixture thereof with at least one chain extender mixture, and (3) at least one polyisocyanate.
• the invention also comprising a NO2-PED synthesized from chemically recycled monomers derived from the decomposition of post-consumer polyethylene.
• the resulting TPU’s provide a sustainable alternative to bio- or petrochemical -based TPU’s.
• thermoplastic polyurethane elastomer composition comprising the reaction products of: at least one nitro-substituted polyester diol (NO2-PED), and at least one polyisocyanate, and further comprising the reaction product with at least one chain extender.
• NO2-PED nitro-substituted polyester diol
• NO2-PED has the formula: wherein n is 0-14, y is 1-100, X is H or NO2, and R is alkylenyl, alkylenyl with one or more CEb groups substituted by -0-, cycloalkylenyl, or arylenenyl, wherein at least on X is NO2.
• R is alkylenyl. In some embodiments, R is ethylenyl, propylenyl, isopropylenyl, butylenyl, pentylenyl, hexylenyl, heptylenyl, or octylenyl.
• R is alkylenyl, wherein one or more CEb groups are substituted by -0-.
• R is -(CH 2 )o-0-(CH 2 )o-, CH 3 -0-(CH 2 )o-0-(CH 2 ) 0 - CH 3 ,
• R is arylenyl or aralkylenyl.
• the N0 2 -PED before reaction has a molecular weight of
• the chain extender is a dihydroxyalkane or dihydroxycycloalkane.
• the chain extender is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3 -propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, neo-pentyl glycol, 1,4-cyclohexanedimethanol, 1,4-dihydroxy cyclohexane, or mixtures thereof.
• the chain extender is an alkylene or aralkylene diamine.
• the chain extender is ethylene diamine, hexamethylene diamine, 1,4- cyclohexanylene diamine, or mixtures thereof.
• the chain extender is an aromatic diamine.
• the aromatic diamine is benzidine, dihydroxymethoxy hydroquinone, toluene diamine, diaminodiphenyl methane, phenylene diamine, or mixtures thereof.
• the chain extender is hydrazine.
• the chain extender is an amino alcohol. In some embodiments, the chain extender is ethanolamine, N-methylethanolamine, N- butylethanolamine, N-oleoylethanolamine, N-cyclohexylisopropanolamine, or mixtures thereof.
• the chain extender is a substituted aromatic diamine.
• the chain extender is 4,4'-methylene-bis(o-chloroaniline), 4,4'- methylenebis(3-chloro-2,6-diethylaniline), or mixtures thereof.
• thermoplastic polyurethane elastomer composition further comprises at least one crosslinking agent.
• the crosslinking agent is glycerine, trimethylolpropane, diethanolamine, triethanolamine, or mixtures thereof.
• the ratio of polyisocyanate to active hydrogen containing group is from 0.9-1.5.
• the isocyanate is 4,4'-diisocyanatodiphenylmethane (4,4-)
• MDI 2,4'-diisocyanato diphenylmethane
• 2,4'-MDI 2,4'-diisocyanato diphenylmethane
• p-phenylene diisocyanate 1,3- bis(isocyanatomethyl)cyclohexane, 1,4-diisocyanato cyclohexane, hexamethylene diisocyanate, isophorone diisocyanate, 1,5 -naphthalene diisocyanate, 3,3'-dimethyl-4,4'- biphenyl diisocyanate, 4,4'-diisocyanato-dicyclohexylmethane, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, or mixtures thereof.
• the isocyanate is 4,4'-MDI or 2,4'-MDI.
• the composition comprises one or more additives.
• the one or more additives comprise at least one light stabilizer, UV stabilizer, or mixtures thereof.
• the one or more additives are an inorganic filler, organic filler, or mixtures thereof.
• the one or more additives are at least one inorganic filler that is a silicate mineral, metal oxide, metal salt, clay, metal silicate, glass fiber, natural fibrous material, synthetic fibrous mineral, or mixtures thereof.
• the additive is an organic filler that is carbon black, fullerene, carbon nanotubes, biochar, melamine colophony, cellulose fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, polyester fibers based on aromatic and/or aliphatic dicarboxylic acid esters, carbon fibers, or mixtures thereof.
• the fillers are present in 0.5-30 percent by weight of the composition.
• the filler comprises at least one flame retardant.
• the at least one flame retardant is an organic phosphate, metal polyphosphate, metal oxide, metal salt, cyanuric acid derivative, or mixtures thereof.
• the at least one flame retardant is present in in 500 to 4000 ppm in the composition.
• the composition comprises a foaming agent.
• the foaming agent is at least one of water, pentane, cyclopentane, a hydrofluorocarbon, or mixtures thereof.
• the nitro- substituted polyester diols are esters of: a. oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, ClO-dicarboxylic acid, Cll-dicarboxylic acid, C12-dicarboxylic acid, C13-dicarboxylic acid, C14-dicarboxylic acid and C15-dicarboxylic acid, and b. at least one C8-C20 dicarboxylic acid substituted with a single nitro group; and at least one polyol.
• the at least one polyol is a Ci-s did.
• the composition comprises 20-80% by weight of the nitro- substituted polyester diol.
• the composition further comprises the reaction products of at least one polyester diol not substituted with a nitro group, and at least one polyisocyanate, and further comprising the reaction product with at least one chain extender.
• compositions comprising reacting: at least one nitro-substituted polyester diol, at least one polyisocyanate and at least one chain extender.
• the reaction conditions comprise a temperature of 25 to
• thermoplastic polyurethane elastomer composition made by the methods described herein.
• thermoplastic polyurethane elastomer composition is in the form of a foam containing:
• the method further comprises reacting at least one polyester diol not substituted with a nitro group.
• the dicarboxylic acids used to make the polyester diol and nitro-polyester diol are esters of: a. oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, ClO-dicarboxylic acid, Cll-dicarboxylic acid, C12-dicarboxylic acid, C13-dicarboxylic acid, C14-dicarboxylic acid and C15-dicarboxylic acid, and b. at least one C8-C20 dicarboxylic acid substituted with a single nitro group; and at least one diol.
• the at least one diol is a Ci-s diol.
• FIG. 1 depicts a bar graph showing the wt% of the dicarboxylic acids in the composition comprising nitro- substituted dicarboxylic acids.
• the term “comprising” or “comprises” is used in reference to compositions, methods, systems, articles of manufacture, and respective component s) thereof, that are useful to an embodiment, yet open to the inclusion of unspecified elements, whether useful or not. It will be understood by those within the art that, in general, terms used herein are generally intended as “open” terms (e.g., the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes but is not limited to,” etc.).
• the term “comprising” or “comprises” means that other elements can also be present in addition to the defined elements presented.
• the use of “comprising” indicates inclusion rather than limitation.
• the open-ended term “comprising” as a synonym of terms such as including, containing, or having, is used herein to describe and claim the invention, the present invention, or embodiments thereof, may alternatively be described using alternative terms such as “consisting of’ or “consisting essentially of’.
• Each group member can be referred to and claimed individually or in any combination with other members of the group or other elements found herein.
• One or more members of a group can be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is herein deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended claims.
• substituted refers to independent replacement of one or more (typically 1, 2, 3, 4, or 5) of the hydrogen atoms on the substituted moiety with substituents independently selected from the group of substituents listed below in the definition for “substituents” or otherwise specified.
• a non-hydrogen substituent can be any substituent that can be bound to an atom of the given moiety that is specified to be substituted.
• substituents include, but are not limited to, acyl, acylamino, acyloxy, aldehyde, alicyclic, aliphatic, alkanesulfonamido, alkanesulfonyl, alkaryl, alkenyl, alkoxy, alkoxycarbonyl, alkyl, alkylamino, alkylcarbanoyl, alkylene, alkylidene, alkylthios, alkynyl, amide, amido, amino, amidine, aminoalkyl, aralkyl, aralkylsulfonamido, arenesulfonamido, arenesulfonyl, aromatic, aryl, arylamino, arylcarbanoyl, aryloxy, azido, carbamoyl, carbonyl, carbonyls including ketones, carboxy, carboxylates, CF3, cyano (CN), cycloalkyl, cycloalky
• Substituents may be protected as necessary and any of the protecting groups commonly used in the art may be employed.
• Non-limiting examples of protecting groups may be found, for example, in Greene and Wuts, Protective Groups in Organic Synthesis, 44 th . Ed., Wiley & Sons, 2006.
• carboxy means the radical — C(0)0 — . It is noted that compounds described herein containing carboxy moiety can include protected derivatives thereof, i.e., where the oxygen is substituted with a protecting group. Suitable protecting groups for carboxy moieties include benzyl, tert-butyl, methyl, ethyl, and the like. The term “carboxyl” means -COOH.
• alkylenyl refers to a divalent form of an alkyl group.
• the alkyleneyl group is a C3-8 alkyleneyl group.
• alkylenyl groups include methylenyl, ethylenyl, propylenyl, isopropylenyl, butylenyl, pentylenyl, and hexyl enyl groups.
• arylenyl refers to a divalent form of an optionally substituted aryl group. In one embodiment, the arylenyl is a divalent form of an optionally substituted phenyl. In one embodiment, the arylenyl is a divalent form of phenyl.
• Non-limiting exemplary alkylenyl groups include:
• cycloalkylenyl refers to a divalent form of a C3-8 cycloalkyl group.
• cycloalkylenyl groups include 1,2-cyclobutenyl, 1,3-cyclobutenyl, 1,2- cyclopentenyl, 1,3-cyclopentenyl, 1,2-cyclohexenyl, 1,3-cyclohexenyl, and 1,4- cyclohexenyl.
• dihydroxycycloalkane refers to a C3-8 cycloalkyl group substituted by two hydroxyl groups.
• dihydroxy cycloalkanes include 1,2- dihydroxycyclobutane, 1,3-dihydroxycyclobutane, 1,2-dihydroxy cyclopentane, 1,3- dihydroxycyclopentane, 1,2-dihydroxy cyclohexane, 1,3-dihydroxycyclohexane, and 1,4- dihydroxy cyclohexane.
• polymer means a substance, chemical compound or mixture of compounds, that has a molecular structure consisting chiefly or entirely of a large number of similar units (e.g., monomer units) bonded together.
• linear polymer is also called straight-chain because it consists of a long string of carbon-carbon bonds; branching polymer has branches at irregular intervals along the polymer chain; cross linking polymer contains branches that connect polymer chains, via covalent, ionic, or H- bonding; optionally substituted polymer is a polymer that contains functionality at random points along the hydrocarbon chain backbone where one or more of the hydrogen atoms linked to the chain backbone may be, but are not required to be substituted with a substituent independently selected from the group of substituents provided herein in the definition for “substituents” or otherwise specified.
• Such polymers are said to be optionally substituted because they generally do not exhibit a regular substitution pattern along the chain backbone; addition polymer is formed by adding monomers to a growing polymer chain; condensation polymer is formed when a small molecule condenses out during the polymerization reaction; homopolymer is formed by polymerizing a single monomer; copolymer is formed by polymerizing more than one monomer; synthetic polymer is synthesized through chemical reactions; natural polymer is originated in nature and can be extracted; biopolymer is produced by living organisms, modified or natural; organic polymers are polymers that contain carbon atoms in the backbone of the polymer chain.
• oligomer means a substance, chemical compound or mixture of compounds that has a molecular structure consisting chiefly or entirely of a few number of similar units (e.g., monomer units) bonded together.
• plastic means a synthetic material comprising a wide range of organic polymers such as polyolefins, polyesters, polyamides, etc., that can be molded into shape while soft and then set into a rigid, semi-elastic, or elastic form.
• thermoplastic polyurethane elastomers made starting with a dicarboxylic acid composition containing nitro- substituted dicarboxylic acids.
• Nitro-substituted dicarboxylic acid compositions may be prepared according to
• the nitro- substituted dicarboxylic acids produced are in admixture with other dicarboxylic acids.
• the process comprises: a. adding polyethylene (PE) to a reaction vessel; b. adding aqueous nitric acid (HNO3) to the reaction vessel to give a mixture, wherein the wt. ratio of PE to aqueous nitric acid is greater than 1 :3; and c. subjecting the mixture obtained in b. to conditions effective to decompose the PE to produce the dicarboxylic acids and nitro- substituted dicarboxylic acids.
• PE polyethylene
• HNO3 aqueous nitric acid
• the nitric acid may have a concentration of 10-90 wt%. In some embodiments, the nitric acid has a concentration of about 67 to 90 wt%. In some embodiments, the weight ratio of PE to nitric acid is 1 : 10 to 1 : 100.
• a catalyst is added to the reaction such as a zeolite, alumina, silico-alumino-phosphate, sulfated zirconia, zinc oxide, titanium oxide, zirconium oxide, niobium oxide, iron carbonate, calcium carbide, or combinations thereof. In some embodiments, the conditions effective comprise a temperature range of about 60 °C to about 200 °C.
• the conditions effective comprise an initial pressure of 0-1000 psi. In some embodiments, the conditions effective comprise a batch process with a residence time in the reaction vessel of about 1 hour to about 10 hours. In some embodiments, the conditions effective comprise a continuous process.
• the dicarboxylic acids and nitro-dicarboxylic acids are then isolated, for example, by filtration of the mixture and evaporation of the nitric acid, e.g., under reduced pressure.
• the dicarboxylic acids and nitro-dicarboxylic acids may then be esterified, e.g., in the presence of an acid catalyst such as hydrochloric or sulphuric acids in the presence of an alcohol, e.g., a Ci-4 alcohol, to give the corresponding dicarboxylic and nitro-dicarboxylic acid Ci-4 esters.
• an acid catalyst such as hydrochloric or sulphuric acids
• an alcohol e.g., a Ci-4 alcohol
• the Ci-4 esters are methyl, ethyl, propyl, butyl, or pentyl esters.
• succinic acid is present in an amount of from about 10 to about 25 wt%
• glutaric acid is present in an amount of from about 11 to about 25 wt%
• adipic acid is present in an amount of about 14 to about 22 wt%
• pimelic acid is present in an amount of about 10 to about 20 wt%
• azelaic acid is present in an amount of about 3 to about 10 wt%, or an equivalent amount of the esters thereof
• oxalic acid is present in an amount up to 10 wt%
• if present suberic acid is present in an amount of about 5 to about 16 wt%
• sebacic acid is present in an amount of about 1 to about 15 wt%
• undecanedioic acid is present in an amount of about 1 to about 8 wt%
• dodecanedioic acid is present up to about 5 wt%, if present tridecanedio
• succinic acid is present in an amount of from about 15 to about 19 wt%
• glutaric acid is present in an amount of from about 17 to about 21 wt%
• adipic acid is present in an amount of about 16 to about 20 wt%
• pimelic acid is present in an amount of about 13 to about 17 wt%
• azelaic acid is present in an amount of about 4 to about 8 wt%, or an equivalent amount of the esters thereof
• oxalic acid is present in an amount up to 10 wt%
• if present suberic acid is present in an amount of about 9 to about 13 wt%
• sebacic acid is present in an amount of about 5 to about 9 wt%
• undecanedioic acid is present in an amount of about 2 to about 4 wt%
• dodecanedioic acid is present in an amount of about 1 to about 3 wt%, if present tride
• succinic acid is present in an amount of from about 5 to about 40 wt%
• glutaric acid is present in an amount of from about 8 to about 27 wt%
• adipic acid is present in an amount of about 10 to about 29 wt%
• pimelic acid is present in an amount of about 10 to about 20 wt%
• azelaic acid is present in an amount of about 1 to about 13 wt%, or an equivalent amount of the esters thereof
• oxalic acid is present in an amount up to 10 wt%
• if present suberic acid is present in an amount of to about 4 to about 20 wt%
• sebacic acid is present up to about 12 wt%
• undecanedioic acid is present up to about 8 wt%
• dodecanedioic acid is present up to about 5 wt%
• tridecanedioic acid is present up to about 4
• the dicarboxylic acids further comprise at least one C8-C20 dicarboxylic acid substituted with a single nitro group or the esters thereof.
• the nitro- substituted C8-C20 dicarboxylic acids may be substituted in the 2-, 3-, 4-, 5-, 6-, 7-, or 8- position of the dicarboxylic acid.
• At least one nitro-substituted dicarboxylic acid is 2-nitro- suberic acid, 2-nitro-azelaic acid, 2-nitro-sebacic acid, 2-nitro-undecanedioic acid, 2- nitro-dodecanedioic acid, 2-nitro-brassylic acid, 2-nitro-tetradecanedioic acid, 2-nitro- pentadecanedioic acid, 2-nitro-hexadecanedioic acid, 2-nitro-heptadecanedioic acid, 2- nitro-octadecanedioic acid, 2-nitro-nonadecanedioic acid, or 2-nitro-icosanedioic acid, or the esters thereof.
• the dicarboxylic acids comprise: a. oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, ClO-dicarboxylic acid, Cll-dicarboxylic acid, C12-dicarboxylic acid, C13-dicarboxylic acid, C14-dicarboxylic acid and C15-dicarboxylic acid, or the esters thereof, and b. at least one C8-C20 dicarboxylic acid substituted with a single nitro group, or the esters thereof.
• the at least one C8-C20 dicarboxylic acid substituted with a single nitro group is nitro-suberic acid, nitro-azelaic acid, nitro-sebacic acid, nitro- undecanedioic acid, nitro-dodecanedioic acid, nitro-brassylic acid, nitro-tetradecanedioic acid, nitro-pentadecanedioic acid, nitro-hexadecanedioic acid, nitro-heptadecanedioic acid, nitro-octadecanedioic acid, nitro-nonadecanedioic acid, or nitro-icosanedioic acid, or the esters thereof.
• the C8-C20 dicarboxylic acid is 2-nitro- suberic acid, 2-nitro-azelaic acid, 2-nitro-sebacic acid, 2-nitro-undecanedioic acid, 2- nitro-dodecanedioic acid, 2-nitro-brassylic acid, 2-nitro-tetradecanedioic acid, 2-nitro- pentadecanedioic acid, 2-nitro-hexadecanedioic acid, 2-nitro-heptadecanedioic acid, 2- nitro-octadecanedioic acid, 2-nitro-nonadecanedioic acid, or 2-nitro-icosanedioic acid, or the esters thereof.
• the C8-C20 dicarboxylic acid is 3 -nitro-suberic acid, 3 -nitro-azelaic acid, 3 -nitro-sebacic acid, 3-nitro-undecanedioic acid, 3 -nitro- dodecanedioic acid, 3-nitro-brassylic acid, 3-nitro-tetradecanedioic acid, 3-nitro- pentadecanedioic acid, 3-nitro-hexadecanedioic acid, 3-nitro-heptadecanedioic acid, 3- nitro-octadecanedioic acid, 3-nitro-nonadecanedioic acid, or 3-nitro-icosanedioic acid, or the esters thereof.
• the C8-C20 dicarboxylic acid is 4-nitro-suberic acid, 4-nitro-azelaic acid, 4-nitro-sebacic acid, 4-nitro-undecanedioic acid, 4-nitro- dodecanedioic acid, 4-nitro-brassylic acid, 4-nitro-tetradecanedioic acid, 4-nitro- pentadecanedioic acid, 4-nitro-hexadecanedioic acid, 4-nitro-heptadecanedioic acid, 4- nitro-octadecanedioic acid, 4-nitro-nonadecanedioic acid, or 4-nitro-icosanedioic acid, or the esters thereof.
• the C8-C20 dicarboxylic acid is 5-nitro-suberic acid, 5-nitro-azelaic acid, 5-nitro-sebacic acid, 5-nitro-undecanedioic acid, 5-nitro- dodecanedioic acid, 5-nitro-brassylic acid, 5-nitro-tetradecanedioic acid, 5-nitro- pentadecanedioic acid, 5-nitro-hexadecanedioic acid, 5-nitro-heptadecanedioic acid, 5- nitro-octadecanedioic acid, 5-nitro-nonadecanedioic acid, or 5-nitro-icosanedioic acid, or the esters thereof.
• the at least one C8-C20 dicarboxylic acid substituted with a single nitro group is present up to about 70 wt% in the decomposition mixture.
• the nitro-dicarboxylic acid composition comprises the dicarboxylic acids in the amounts shown in Fig. 1.
• the dicarboxylic acids and nitro-dicarboxylic acids are in an ester form. These esters are prepared under esterification conditions. In some embodiments, the dicarboxylic acids are at least partially in the form of esters.
• the esters are methyl esters, ethyl esters, propyl esters, isopropyl esters, butyl esters, isobutyl esters, sec-butyl esters, tert-butyl esters, pentyl esters, or hexyl esters, or combinations thereof.
• the ester is a methyl ester.
• the converting is carried out by esterification or esterifying.
• esters Any suitable esterification conditions known in the art may be used to form the esters.
• the dicarboxylic acids and nitro-dicarboxylic acids can be admixed with at least one alcohol and the admixture heated to cause esterification.
• a mineral acid or organic acid may be added as a catalyst.
• the at least one alcohol is at least one selected from a group consisting of linear alcohol, branched alcohol, cyclic alcohol, and combinations thereof.
• the at least one alcohol is at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, hexanol, and combinations thereof.
• the at least one alcohol is a Ci-Cio alcohol.
• the at least one alcohol is a C1-C4 alcohol.
• the at least one alcohol is methanol.
• the succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid are each independently in an ester form.
• the oxalic acid, suberic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, 2-octenedioic acid, 2-nonenedioic acid, 2-decenedioic acid, and 2-undecenedioic acid are independently in an ester form.
• the 2-nitro-suberic acid, 2-nitro-azelaic acid, 2-nitro- sebacic acid, 2-nitro-undecanedioic acid, 2-nitro-dodecanedioic acid, 2-nitro-brassylic acid, 2-nitro-tetradecanedioic acid, 2-nitro-pentadecanedioic acid, 2-nitro- hexadecanedioic acid, 2-nitro-heptadecanedioic acid, 2-nitro-octadecanedioic acid, 2- nitro-nonadecanedioic acid, and 2-nitro-icosanedioic acid are independently in an ester form.
• the C8-C20 dicarboxylic acid substituted with a single nitro group is in an ester form.
• the C8-C20 dicarboxylic acid substituted with a single nitro group in the form of an ester is nitro-suberic acid, nitro-azelaic acid, nitro-sebacic acid, nitro-undecanedioic acid, nitro-dodecanedioic acid, nitro-brassylic acid, nitro-tetradecanedioic acid, nitro-pentadecanedioic acid, nitro-hexadecanedioic acid, nitro-heptadecanedioic acid, nitro-octadecanedioic acid, nitro-nonadecanedioic acid, or nitro-icosanedioic acid.
• the C8-C20 dicarboxylic acid is 2-nitro- suberic acid, 2-nitro-azelaic acid, 2-nitro-sebacic acid, 2-nitro-undecanedioic acid, 2- nitro-dodecanedioic acid, 2-nitro-brassylic acid, 2-nitro-tetradecanedioic acid, 2-nitro- pentadecanedioic acid, 2-nitro-hexadecanedioic acid, 2-nitro-heptadecanedioic acid, 2- nitro-octadecanedioic acid, 2-nitro-nonadecanedioic acid, or 2-nitro-icosanedioic acid, or the esters thereof.
• the ester form is selected from the group consisting of monoester, diester, multiester, mixed diester, mixed multiester, and combinations thereof.
• multiester as used herein means an ester formed by converting more than one carboxyl group from a dicarboxylic acid form to an ester form under esterification conditions.
• the at least one ester comprises dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, dimethyl undecanedioate, dimethyl dodecanedioate, dimethyl oxalate, dimethyl tridecanedioate, dimethyl tetradecanedioate, dimethyl pentadecanedioate, dimethyl 2-octendioate, dimethyl 2-nonendioate, 2-dimethyl 2- decendioate, dimethyl 2-undecendioate, dimethyl 2-nitro-suberate, dimethyl 2-nitro- azelate, dimethyl 2-nitro-sebacate, dimethyl 2-nitro-undecanedioate, dimethyl 2-nitro- dodecanedioate, dimethyl 2-nitro-brassylate, dimethyl 2-nitro-heptadecanedioate, dimethyl
• the at least one corresponding ester comprises dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, dimethyl undecanedioate, dimethyl dodecanedioate, and combinations thereof.
• the at least one ester comprises of 5-50% dimethyl succinate, 5-50% dimethyl glutarate, 5-50% dimethyl adipate, 5-50% dimethyl pimelate, 0-30% dimethyl suberate, 0-30% dimethyl azelate, 0-20% dimethyl sebacate, 0-10% dimethyl undecanedioate, 0-10% dimethyl dodecanedioate, and combinations thereof.
• the at least one corresponding ester is comprises of 5-50% dimethyl succinate, 5-50% dimethyl glutarate, 5-50% dimethyl adipate, 5-50% dimethyl pimelate, 0-30% dimethyl suberate, 0-30% dimethyl azelate, 0-20% dimethyl sebacate, 0- 10% dimethyl undecanedioate, 0-10% dimethyl dodecanedioate, and combinations thereof.
• the esterification mixture comprises a composition comprising at least one of dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, dimethyl undecanedioate, dimethyl dodecanedioate, and combinations thereof.
• the esterification mixture comprises a composition comprising at least one of 5-50% dimethyl succinate, 5-50% dimethyl glutarate, 5-50% dimethyl adipate, 5-50% dimethyl pimelate, 0-30% dimethyl suberate, 0-30% dimethyl azelate, 0-20% dimethyl sebacate, 0-10% dimethyl undecanedioate, 0-10% dimethyl dodecanedioate, and combinations thereof.
• the esterification mixture comprises at least one of dimethyl succinate in an amount of from about 5 to about 18 wt%, dimethyl glutarate in an amount of from about 8 to about 28 wt%, dimethyl adipate in an amount of about 10 to about 29 wt%, dimethyl pimelate in an amount of about 10 to about 20 wt%, and dimethyl azelate in an amount of about 8 to about 13 wt%, and combinations thereof.
• the esterification mixture comprises at least one of dimethyl oxalate in an amount up to 10 wt%, dimethyl suberate in an amount of about 9 to about 20 wt%, dimethyl sebacate in an amount of about 1 to about 10 wt%, dimethyl undecanedioate in an amount of about 1 to about 8 wt%, dimethyl dodecanedioate up to about 5 wt%, dimethyl tridecanedioate up to about 4 wt%, dimethyl tetradecanedioate up to about 2 wt%, and dimethyl pentadecanedioate up to about 0.4 wt%, and combinations thereof.
• the esterification mixture comprises at least one of dimethyl succinate in an amount of from about 5 to about 40 wt%, dimethyl glutarate in an amount of from about 8 to about 27 wt%, dimethyl adipate in an amount of about 10 to about 29 wt%, dimethyl pimelate in an amount of about 10 to about 20 wt%, and dimethyl azelate in an amount of about 1 to about 13 wt%, and combinations thereof.
• the esterification mixture comprises at least one of dimethyl oxalate in an amount up to 10 wt%, dimethyl suberate in an amount of to about 4 to about 20 wt%, dimethyl sebacate up to about 10 wt%, dimethyl undecanedioate up to about 8 wt%, dimethyl dodecanedioate up to about 5 wt%, dimethyl tridecanedioate up to about 4 wt%, dimethyl tetradecanedioate up to about 2 wt%, and dimethyl pentadecanedioate up to about 0.4 wt%, and combinations thereof.
• the esters are of: a. oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, ClO-dicarboxylic acid, Cll-dicarboxylic acid, C12-dicarboxylic acid, C13-dicarboxylic acid, C14-dicarboxylic acid and C15-dicarboxylic acid, and b. at least one C8-C20 dicarboxylic acid substituted with a single nitro group; and at least one polyol.
• the method further comprises separating the at least one corresponding ester.
• the separating is carried out by distillation.
• the distillation is at least one selected from the group consisting of simple distillation, fractional distillation, vacuum distillation, azeotropic distillation, co distillation, and combinations thereof.
• the method further comprises converting the at least one compound containing at least one carboxyl group from the ester form to an acid form (e.g., converting the ester form back to the acid form).
• the converting of the ester form to the acid form is performed under ester hydrolysis conditions.
• the invention also provides nitro-functionalized polyester diols (NO2-PED) by reacting the dicarboxylic acids and nitro-dicarboxylic acids or esters thereof with a diol.
• NO2-PED nitro-functionalized polyester diols
• Polyester diols have the formula: wherein n is 0-14, y is 1-100, X is H or NO2, and R is alkylenyl, alkylenyl with one or more CH2 groups substituted by -O-, cycloalkylenyl, or arylenenyl, wherein at least one X is NO2.
• R is ethylenyl, propylenyl, isopropylenyl, butylenyl, pentylenyl, hexylenyl, heptylenyl, or octylenyl.
• R is alkylenyl, wherein one or more CH2 groups are substituted by -O-.
• R is - (CH 2 )O-0-(CH 2 )O-, CH3-0-(CH2)O-0-(CH 2 )O- CH 3 , (CH 3 CH(0H)CH2)20, wherein o is 2- 4.
• polyester diol before reaction with the isocyanate has a molecular weight of 300-10,000 g/mol.
• diols include, for instance, 1,2-propanediol, 1,3-propanediol, 1,4- butanediol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9- nonanediol, 1,10-decandiol, ethylene glycol, di ethylene glycol, tri ethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, glycerol, trimethylol ethane, trimethylol propane, neo-pentyl glycol, pentaerythritol, dipentaerythritol, sorbitol, 2- methyl-1, 3-propane diol, 2, 2-dimethyl- 1,3 -propanediol, 2-ethyl- 1,3 -propanediol
• the diols are Ci-8 diols, e.g. or Ci-4 diols, for instance diethylene glycol, 1,2-propanediol, and 1,3- propanediol.
• the NCh-PEDs are prepared by reacting the dicarboxylic acids and nitro- carboxylic acids or esters thereof under suitable reaction conditions.
• the NCh-PEDs are synthesized according to the following general procedure and as represented in Scheme 1: The dicarboxylic acid mixture is combined with diol (e.g.
• 1,6-hexanediol 1,6-hexanediol
• a catalytic amount of concentrated sulfuric acid or other suitable catalyst may vary between 0.2 mole percent (mol%) to 4 mol%.
• the mixture is heated while stirring in a pre-warmed oil bath at 100-110 °C for 2- 4 hours under atmospheric pressure, followed by application of reduced pressure ( ⁇ 19 mbar) for 1-2 hours.
• the product is cooled under vacuum, and characterized by ATR- FTIR analysis and end group titration (total acid number and hydroxyl number).
• Polyester diols stored outside of a desiccator for prolonged periods are dried prior to use by overnight incubation in a vacuum oven at 80 °C, or by bubbling dry inert gas (e.g. argon) through the polyol at >100 °C while simultaneous applying vacuum for 1 hour, followed by storage in an ambient pressure desiccator.
• dry inert gas e.g. argon
• the reaction is typically carried out at atmospheric pressure, but other pressures may be used. OH 1 atm, then ⁇ 1 atm
• n 0-20, and y is 1-100. In some embodiments, y is 1-30.
• the NCh-PEDs are prepared by reacting the esters of the dicarboxylic acids and nitro-dicarboxylic acids with the polyol also in the presence of a suitable catalyst such as sulfuric acid or other mineral acid according to Scheme 2.
• a suitable catalyst such as sulfuric acid or other mineral acid according to Scheme 2.
• n is 0-20, and y is 1-100. In some embodiments, y is 1-30.
• the catalyst may be hydrochloric acid, sulphuric acid, or other mineral acid.
• the catalyst may be dibutyl tin(IV) dilaurate in an organic solvent such as heptane.
• the mixture may be heated while stirring at 100-130 °C for 1-20 hours under atmospheric pressure and the alcohol by-product (e.g., methanol) and organic solvent, if used (e.g., heptane), is evaporated and removed from the reactor. In some embodiments, this is followed by application of reduced pressure ( ⁇ 19 mbar) for 1-20 hours. Removal of the alcohol by-product and organic solvent may also be removed by bubbling an inert gas though the mixture while applying a vacuum for 1 hour.
• alcohol by-product e.g., methanol
• organic solvent if used
• the number average molecular weight of the NCh-PEDs range from 300 to 10000 g/mol. In some embodiments, the number average molecular weight is about 500 to about 4000 g/mol.
• TPU Thermoplastic Polyurethanes
• TPUs may be prepared by a one-step or two-step method.
• the NO2-PED and chain extender are blended in a reaction vessel.
• the polyisocyanate is slowly added the the vessel while stirring vigorously.
• the reaction proceeds at temperatures 60-120 °C for 2.5 hours.
• the resulting TPU is then cast into a pre-heated silicone mold and cured, for example, 20 to 48 hours at a temperature of 80 to 120 °C.
• the two-step method involves reacting the NCh-PEDs with a polyisocyanate to give a TPU pre-polymer followed by chain extension to yield a finished TPU elastomer.
• the NO2-PED is reacted with a polyisocyanate at temperatures up to 80 °C.
• a catalyst and chain extender is then added while stirring rapidly and allowed to react at temperatures up to 120 °C.
• the catalyst may be any tin laureate, or amine catalyst such as DABCO or triethylamine at a wt% of 0.05 to 1.0 compared to the NCh-PEDs.
• the NO2-PED can be 20-80 wt% of the chain extended TPU.
• the polyisocyanate can be 20-80 wt% of the chain extended TPU.
• the chain extender can be 1-20 wt% of the chain extended TPU.
• the chain extended TPU is then poured into a mold and allowed to cure, for example, 20 to 48 hours at a temperature of 80 to 120 °C.
• polyisocyanates include, for instance, 2,4-tolylene diisocyanate, 2,6- tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5- naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, methylenebis(4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, bis(2- is
• the polyisocyanate is 4,4'-diisocyanatodiphenylmethane
• the ratio of polyisocyanate to active hydrogen containing group is from 0.9-1.5.
• the NCO index is defined as the number of equivalents of isocyanate, divided by the total number of equivalents of active hydrogen, multiplied by 100.
• the NCO index is represented by the following formula: 100
• the TPU pre-polymer is then reacted with a chain extender.
• chain extenders include diols such as 1,2-propanediol, 1,3 -propanediol, 1,4-butanediol, 1,2- butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10- decandiol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, glycerol, trimethylol ethane, trimethylol propane, neo-pentyl glycol, pentaerythritol, dipentaerythritol, sorbitol, 2-methyl- 1,3 -propane diol, 2.2-dimethyl-l, 3-propane
• the polyols are Ci-8 polyols, e.g. Ci-8 diols or Ci-4 diols, for instance diethylene glycol, 1,2-propane diol, and 1,3-propane diol.
• the chain extender is a dihydroxyalkane or dihydroxycycloalkane.
• the chain extender is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propane diol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, neo-pentyl glycol, 1,4-cyclohexanedimethanol, 1,4-dihydroxy cyclohexane, or mixtures thereof.
• the chain extender is an alkylene or aralkylene diamine.
• the chain extender is ethylene diamine, hexam ethylene diamine, 1,4- cyclohexanylene diamine, or mixtures thereof. In some embodiments, the chain extender is an aromatic diamine. In some embodiments, the chain extender is benzidine, dihydroxymethoxy hydroquinone, toluene diamine, diaminodiphenyl methane, phenylene diamine, or mixtures thereof. In some embodiments, the chain extender is hydrazine. In some embodiments, the chain extender is an amino alcohol.
• the chain extender is ethanolamine, N-methylethanolamine, N-butylethanolamine, N- oleoylethanolamine, N-cyclohexylisopropanolamine, or mixtures thereof.
• the chain extender is a substituted aromatic diamine.
• the chain extender is 4,4’-methylene-bis(o-chloroaniline), 4,4’- methylenebis(3-chloro-2-6-diethylaniline, or mixtures thereof.
• the optional additives include further crosslinking agents, oligomers, light stabilizers, UV stabilizers, inorganic and organic fillers, flame retardants, dispersants, foaming agents, reactive diluents, free radical photoinitiators, cationic photoinitiators, and other additives.
• the crosslinking agent is glycerine, trimethylolpropane, diethanolamine, triethanolamine, or mixtures thereof.
• further oligomers include, for instance, poly ethers, polyesters, polycarbonates, polyacrylates, and copolymers thereof.
• the further oligomers may comprise one or more (e.g. two or more) hydroxy groups, comprise one or more (e.g. two or more) ethylenically unsaturated groups, and/or comprise one or more (e.g. two or more) epoxy groups.
• the present compositions comprise, relative to the total weight of the composition, 0-60 wt% of further oligomers, e.g. 5-40 wt%.
• the light and UV stabilizers include 2-(2'-hydroxy-5'-tert- octylphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5- chlorobenzotri azole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5- bis(a,a-di methyl benzyl )phenyl]-2//-benzotri azole, 2,2'-methylenebis(4-cumyl-6- benzotriazolephenyl), 2,2'-p-phenylenebis(l,3-benzoxazin-4-one), and mixtures thereof.
• the inorganic filler comprises a silicate mineral, metal oxide, metal salt, clay, metal silicate, glass fiber, natural fibrous material, synthetic fibrous mineral, or mixtures thereof.
• the organic filler comprises carbon black, fullerene, carbon nanotubes, biochar, melamine colophony, cellulose fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, polyester fibers based on aromatic and/or aliphatic dicarboxylic acid esters, carbon fibers, or mixtures thereof.
• the fillers are present in 0.5-30 percent by weight of the composition.
• the flame retardant is an organic phosphate, metal polyphosphate, metal oxide, metal salt, cyanuric acid derivative, or mixtures thereof.
• flame retardant is present in in 10 to 35 percent by weight of the composition.
• the dispersant comprises styrene, an acrylic ester, a di- and tri-acrylate/methacrylate, an ester acrylate/methacrylate, urethane or urea acrylate/methacrylate, or mixtures thereof.
• the foaming agent is at least one of water, pentane, cyclopentane, a hydrofluorocarbon, or mixtures thereof.
• Examples of reactive diluents include monofunctional monomers and polyfunctional monomers.
• Examples of monofunctional monomers include monomers containing a vinyl group, such as N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl imidazole, vinyl pyridine; isobornyl(meth)acrylate, bornyl(meth)acrylate, tricyclodecanyl(meth)acrylate, dicyclopentanyl(meth)acrylate, dicyclopentenyl(meth)acrylate, cyclohexyl(meth)acrylate, benzyl(meth)acrylate, 4- butylcyclohexyl(meth)acrylate, acryloyl morpholine, 2-hydroxyethyl(meth)acrylate, 2- hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, methyl (meth)acryl ate, ethyl(meth)acrylate, propyl(meth)
• polyfunctional monomers include monomers containing two or more
• (meth)acrylate groups such as trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neo-pentyl glycol di(meth)acrylate, trimethylolpropanetrioxyethyl (meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(2- hydroxyethyl)isocyanurate di(meth)acrylate, tricyclodecane diyl dimethyl di(meth)acrylate, and di(meth)acrylate of a diol which is an ethylene oxide or propylene oxide adduct to bisphenol A,
• the compositions comprise, relative to the total weight of the composition, at least 10 wt% of one or more reactive diluents, e.g. at least 20 wt% or at least 30 wt%.
• the compositions generally comprise less than 90 wt% of one or more reactive diluents, e.g. less than 75 wt% or less than 50 wt%.
• free radical photo initiators include benzophenones (e.g. benzophenone, alkyl-substituted benzophenone, or alkoxy-substituted benzophenone); benzoins, e.g.
• Free radical photoinitiators are particularly useful if the composition comprises ethylenically unsaturated components, for instance acrylates or methacrylates.
• the compositions comprise, relative to the total weight of the composition, 0-10 wt% of one or more free radical photoinitiators, e.g. 0.5-7.5 wt%.
• Examples of cationic photoinitiators include, for instance, onium salts with anions of weak nucleophilicity.
• Examples include halonium salts, iodosyl salts or sulfonium salts, such as are described in published European patent application EP 153904 and WO 98/28663, sulfoxonium salts, such as described, for example, in published European patent applications EP 35969, 44274, 54509, and 164314, or diazonium salts, such as described, for example, in U.S. Pat. Nos. 3,708,296 and 5,002,856.
• additives include antioxidants, dyes, wetting agents, antifoaming agents, thickening agents, photosensitizers, solvents (preferably in amounts less than 20 wt%, e.g. less than 10 wt%, less than 5 wt%, or about 0 wt%), and metallic-, organic-, inorganic-, or organic/inorganic hybrid fillers (e.g. silica particles, glass beads, or talc).
• the size of the fillers may vary and can be, for instance, in the nanometer range or in the micrometer range.
• the present compositions comprise, relative to the total weight of the composition, less than 20 wt% of fillers, e.g. less than 10 wt%, less than 5 wt%, or about 0 wt%.
• Additional additives include colorants such as titanium dioxide and carbon black.
• the TPUs are made by a process that comprises reacting under the following conditions: (a) a polyester comprising at least one nitro- substituted polyester diol, and
• the reaction conditions comprise a temperature of 25 to
• the polyester comprising at least one nitro-substituted polyester diol further comprises at least one polyester diol not comprising a nitro group.
• the TPU foams are made by a process comprising reacting under reaction conditions:
• the TPUs are useful in a wide variety of applications.
• the compositions are useful for preparing molded articles such as soles for footwear, hard solid plastics such as for electronic instrument bezels and structural parts, flexible plastics such as straps and bands, and for seals, gaskets, durable elastomeric wheels and tires, automotive suspension bushings, and electrical insulating parts.
• the compositions are useful for 3D printing when the compositions are extruded into filament.
• the compositions can be pelletized and expanded to yield expanded TPU foams for footwear applications.
• DCAs Dicarboxylic acids employed in polyester diol synthesis were obtained from the accelerated thermal oxidative decomposition (ATOD) of polyethylene plastic and consist of a mixture of linear aliphatic DCAs with carbon numbers ranging from 4-24 carbons. The mixture also contains DCAs bearing one or more nitro functional groups along the aliphatic linker. Average DCA molecular weights for the purposes of chemical synthesis were determined by titration with aqueous sodium hydroxide with phenolphthalein as indicator (acid number determination). Other reagents and equipment were obtained from commercial sources and used as received, unless otherwise indicated. The materials used in the examples are as follows:
• T g The glass transition temperature was measured via differential scanning calorimetry (DSC).
• Shore A Hardness was measured according to DIN 533505 in which the hardness is off 3 seconds after the pressure foot comes in contact with the test specimen. The hardness is indicated as Shore A hardness in the following text.
• Tensile Strength is indicated as Shore A hardness in the following text.
• Tensile strength is measured via an Instron Universal Tester using ASTM Type 4 test bars.
• Elongation is measured via an Instron Universal Tester using ASTM Type 4 test bars.
• PED Polyester diol (synthetic mixture of dicarboxylic acids and 1,6-hexanediol)
• NO2-PED Nitro functionalized polyester diol (synthesized from ATOD DCA’s)
• Emerox 14801 Biobased polyester diol (commercially available)
• MDI 4,4'-diphenylamine diisocyanate (commercially available)
• HDI hexamethylene diisocyanate (commercially available)
• 1,4-BD 1,4-butane diol (commercially available)
• DTBL Dibutyltin dilaurate (commercially available)
• Irganox 1076 Phenolic antioxidant (commercially available)
• Irgafos 168 Phosphite antioxidant (commercially available)
• Tinuvin 234 Benzotrizole UV absorber (commercially available)
• Polyester diols stored outside of a desiccator for prolonged periods were dried prior to use by overnight incubation in a vacuum oven at 80 °C, or by bubbling dry inert gas (e.g. argon) through the polyol at >100 °C while simultaneous applying vacuum for 1 hour, followed by storage in an ambient pressure desiccator.
• dry inert gas e.g. argon
• Specific and non-limiting examples of polyester diols synthesized containing recycled content are presented in Examples 1-4.
• DCA Dicarboxylic acid
• 1,6-hexanediol (26.581 grams, 1 molar equivalent)
• sulfuric acid catalyst (0.131 grams, 1 mol% relative to DCA mix)
• the mixture was heated to 105 °C open to air for 4 hours with stirring, at which point heating and stirring of the reaction melt was continued under applied vacuum ( ⁇ 19 mbar) for 2 more hours.
• the reaction mixture was cooled under vacuum and stored in a desiccator.
• the nitro- containing polyester diol product (PE-1) was characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), 1HNMR, gel permeation chromatography (GPC) and end-group titration (total acid number, and hydroxyl number determination by the acetylation method, Test Method A according to ASTM D-4274- 99).
• the acid number was measured as 4.6 ⁇ 0.3 mg KOH/g sample, the hydroxyl number was 183 ⁇ 9 mg KOH/g sample, the number average molecular weight was determined to be 614 ⁇ 30 g/mol by titration.
• ATOD DCA mixture (42.803 grams, 0.901 molar equivalents) was combined with
• 1,6-hexanediol (31.513 grams, 1 molar equivalent) and concentrated sulfuric acid (98%, 0.229 grams, 1 mol% relative to DCA mix) in a round bottom flask with a Teflon-coated magnetic stir bar.
• the mixture was heated at 105 °C open to air to produce a homogeneous melt for 4 hours, followed by application of vacuum ( ⁇ 19 mbar) with continued heating for 2 additional hours.
• the product was cooled under vacuum and stored in an ambient pressure desiccator.
• the nitro-containing polyester diol product PE-2 was characterized by ATRFTIR, GPC, and end-group titration as in Example 1.
• the acid number was 6.3 ⁇ 0.6 mg KOH/g, the hydroxyl number was 37.4 ⁇ 8.1 mg KOH/g, the number average molecular weight was 2615 g/mol by titration.
• nitro- substituted polyester diols prepared by the methods described above are shown in Table 1.
• Nitro-substituted polyester diols may optionally be synthesized from the corresponding dimethyl esters of DC As obtained from ATOD of polyethylene plastic waste, as depicted in Scheme 2 and described in Examples 3 and 4.
• the starting diester mix is estimated to have an average molecular weight of 177 g/mol.
• a reactor is charged with 100 parts by mass of the diester mix and 107 parts by mass of 1,6-hexanediol and heated to 120 °C. To this mixture are added 6 parts of a 10 wt% solution of dibutyl tin(IV) dilaurate in heptane. The solution is stirred and allowed to react at 120 °C for 17 hours, allowing heptane and evolved methanol to evaporate out of the reactor. The reaction is then cooled to give 146 parts by weight isolated of the product as a clear yellow liquid. GPC analysis in THF vs polystyrene standards indicate Mn 600, PDI 3.49.
• Example 4 (ref: RP1-139D)
• the starting diester mix is estimated to have an average molecular weight of 177 g/mol.
• a reactor is charged with 100 parts by mass of the diester mix and 72 parts by mass of 1,6-hexanediol and heated to 120 °C. To this mixture are added 5.5 parts of a 10 wt% solution of dibutyl tin(IV) dilaurate in heptane. The solution is stirred and allowed to react at 120 °C for 17 hours, allowing heptane and evolved methanol to evaporate out of the reactor. The reaction is then cooled to give 119 parts by weight isolated of the product as a clear yellow liquid.
• GPC analysis in THF vs polystyrene standards indicate Mn 3200, PDI 2.13.
• the parts and percentages referred to in the examples are by weight (pbw) or percentages by height. All samples are prepared identically.
• the diisocyanate, 4,4’-MDI is dried and directly fed into a reaction vessel in excess.
• the PED (compositions shown in Table 2) is added to the excess diisocyanate and allowed to react fully at temperatures up to 60 °C to yield a TPU prepolymer.
• a DTBL catalyst and 2-methyl propane diol (MPD) chain extender are added to the prepolymer while stirring rapidly and allowed to fully react at temperatures up to 100 °C.
• the chain extended TPU is poured into a mold heated to temperatures up to 125 °C.
• the mold is placed in an oven at 100 °C for 24 hours or until the TPU is fully cured.
• the cast elastomers are compression molded into test specimens.
• the post-cured TPU’s are characterized using FTIR, DSC, TGA, Instron Mechanical Testing and a Shore Hardness A Durometer.
• TPU elastomer Example 5 and Comparative Sample A are prepared from the formulations described in Table 2.
• the results in Table 3 show that the presence of nitro groups on the PED backbone results in a TPU with a higher glass transition temperature, higher Shore A Hardness, higher tensile strength, and lower elongation when compared to Sample A.
• Example 6 and Comparative Sample B are prepared using the PEDs described in
• Example 6 1,4-BD and a NO2-PED having a number average molar weight of l.OxlO 3 g/mol derived from the DCA mixture obtained from ATOD are dried and charged into a reaction vessel. Furthermore, 2 wt.% of Sicopal Blue K pigment, 0.3 wt.% of Irganox 1076, and 0.15 wt.% of Irgafos 168 are added to the 1,4-BD/N02-PED mixture. HDI is slowly added while stirring vigorously. The reaction proceeds at 80°C for 2.5 hours. The reaction mixture is poured into a pre-heated silicone mold and cured at 100°C for 24 hours. The cast elastomer is then compression molded into test specimens.
• Comparative Sample B is prepared following the same methodology using a nitro-free polyester diol, Emerox 14801, having a number average molar weight of l.lxlO 3 g/mol.
• the results in Table 5 show the nitro-functionalized TPU derived from aNCE-PED yields a higher Shore A hardness, higher tensile strength, and higher elongation compared to nitro-free PED.
• 1,4-BD and a NO2-PED having a number average molar weight of 1 8xl0 3 g/mol derived from the transesterified NCE-diester mixture are dried and charged into a reaction vessel.
• HDI is slowly added while stirring vigorously.
• the reaction proceeds at 80°C for 2.5 hours.
• the reaction mixture is poured into a pre-heated silicone mold and cured at 100°C for 24 hours.
• the cast elastomer is then compression molded into test specimens.
• HDI is dried and fed into a reaction vessel in excess.
• NO2-PED with a number average molecular weight of 1.3xl0 3 g/mol is blended with 2.0 wt.% carbon black.
• the formulated NO2-PED is then added to the excess diisocyanate and allowed to react fully at temperatures up to 60 °C to yield a TPU prepolymer.
• a DTBL catalyst and MPD are added to the prepolymer while stirring rapidly and allowed to fully react at temperatures up to 100 °C.
• the chain extended TPU is poured into a preheated silicone mold. The mold is placed in an oven at 100 °C for 24 hours or until the TPU is fully cured.
• the cast elastomers are compression molded into test specimens.
• PED with a number average molecular weight of 1.3xl0 3 g/mol is blended with 0.5 wt.% Tinuvin 234, 0.17 wt.% Irgafos 168, and 0.33 wt.% Irganox 1076.
• the formulated NO2- PED is then added to the excess diisocyanate and allowed to react fully at temperatures up to 60 °C to yield a TPU prepolymer.
• a DTBL catalyst and 1,4-BD are added to the prepolymer while stirring rapidly and allowed to fully react at temperatures up to 100 °C.
• the chain extended TPU is poured into a preheated silicone mold. The mold is placed in an oven at 100 °C for 24 hours or until the TPU is fully cured.
• the cast elastomers are compression molded into test specimens.
• a NO2-PED having a number average molecular weight of 500 g/mol was blended with 3.0 wt.% distilled water, 2 wt.% silicone oil, and 1.0 wt.% DTBL catalyst in a flat-bottom polyethylene beaker and mixed. MDI is added directly to the formulated polyol and mixed vigorously for 15 s. The resulting foam was allowed to stabilize at room temperature for 24 hours prior to characterization.

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