WO2024129790A2 - Composition de polyuréthane élastique dégradable - Google Patents

Composition de polyuréthane élastique dégradable Download PDF

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Publication number
WO2024129790A2
WO2024129790A2 PCT/US2023/083707 US2023083707W WO2024129790A2 WO 2024129790 A2 WO2024129790 A2 WO 2024129790A2 US 2023083707 W US2023083707 W US 2023083707W WO 2024129790 A2 WO2024129790 A2 WO 2024129790A2
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Prior art keywords
glycol
fiber
weight
article
polyester
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PCT/US2023/083707
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English (en)
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WO2024129790A3 (fr
Inventor
Nicholas KURLAND
Anthony Mai
Oguzhan CELEBI
Ronald D Bing-Wo
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The Lycra Company Llc
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Publication of WO2024129790A2 publication Critical patent/WO2024129790A2/fr
Publication of WO2024129790A3 publication Critical patent/WO2024129790A3/fr

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
    • 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
    • C08G18/28—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
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene 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
    • C08G18/7664—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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/72—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyureas
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • 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
    • C08G2230/00—Compositions for preparing biodegradable polymers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/04—Dry spinning methods

Definitions

  • the present invention relates to the production of segmented polyurethanes and poly(urethane ureas) with engineered soft segments enhancing the susceptibility to degradation, including but not limited to biodegradation, by incorporation of hydrolytically-unstable polyester glycols into the soft segment, to compositions comprising these polymers and to articles of manufacture produced from these compositions.
  • the present in vention relates to spandex fibers produced from these polymers with the engineered soft segment biodegradation susceptibility and to articles of manufacture produced from these spandex fibers.
  • Biodegradation is a process where substances will decompose into smaller molecules after interactions with natural and biological organisms such as bacteria, fungi, algae and any living organisms.
  • Biodegradable polymers degrade via induced chain scission mediated by biological enzyme activity, whereby weak points in a polymer chain undergo cleavage, leading to a molecular weight reduction and decomposition into the smallest components possible.
  • Composting is also a deliberate biodegradation process where the degradation will lead to a weight loss in a controlled industrial process with tunable conditions such as oxygen and moisture content and temperature. Decomposed products are metabolized and utilized by various microorganisms and converted to carbon dioxide, water and bacterial cell components.
  • US Patent 8,357,767 discloses a high modulus polyurethane composition incorporating a polyester backbone, extended with a linear aliphatic glycol, which was used in extruded articles.
  • Chinese Patent 109338504 discloses use of an easily biodegradable polyester glycol in limited amounts.
  • a polyurethaneurea fiber comprising a glycol, a diisocyanate, and a chain extender wherein the glycol component comprises greater than 50% by weight of a polyester glycol having a number average molecular weight from about 450 to about 3300 and the fiber is degradable.
  • the fiber may yields a normalized recovery force, expressed as the recovery power at 200% elongation of the 5th unload cycle of at least 0.022 centinewtons per deci tex.
  • An article of manufacture comprising a polyurethaneurea fiber comprising a glycol, a diisocyanate, and a chain extender wherein the glycol component comprises greater than 50% by weight of a polyester glycol having a number average molecular weight from about 450 to about 3300 and the fiber is degradable.
  • a composition comprising a glycol component, a diisocyanate, and a chain extender wherein the glycol component comprises a polyester glycol having a number average molecular weight from about 450 to about 3300, a biodegradability enhancing additive in an amount of about 0.1% to about 50% by weight of the composition and the composition is degradable.
  • compositions including a glycol component, a diisocyanate, and a chain extender wherein the glycol component comprises a polyester glycol having a number average molecular weight from about 450 to about 3300, a degradability enhancing additive in an amount of about 0.1% to about 50% by weight of the composition and the composition is degradable
  • a method for degrading spandex includes subjecting one or more compositions, articles, or fibers including the polyurethane urea disclosed herein to conditions resulting in degradation of the polymer structure.
  • Fig. 1 is a Table listing components of fibers and their constituent polymers, in terms of glycol type, glycol molecular weight, %NCO of the capped glycol, and chain extender type.
  • Fig 2 is a Table summarizing biodegradation rates of each fiber example over a 4-week period, utilizing an enzymatic method for screening.
  • Degradation of the fiber occurs with both micro-scale loss of structure of the fiber, resulting in mass loss, and molecular-scale loss of structure of the polymer chains, resulting in molecular weight loss.
  • Molecular weight loss is a more sensitive measure of degradation due to detection thresholds, hence the con-elation between measures, however non-overlap in actual rates.
  • the comparative examples despite having a polyether or polyester base, there is no significant degree of biodegradation depicted.
  • Fig. 3 is a schematic depicting the tabular data from Fig. 2 in terms of molecular weight loss.
  • Fig. 4 is a schematic depicting the tabular data from Fig. 2 in terms of mass loss.
  • Fig. 5 is a schematic depicting the relationship between retractive force (5TM2) and biodegradation rate, as assessed by molecular weight loss.
  • TM2 retractive force
  • biodegradation rate as assessed by molecular weight loss.
  • the fibers including blended glycol, Example 4 and Example 5 both have molecular weight, loss over 10%, while maximizing retractive force characteristics.
  • Fig. 6 is a Table depicting fiber properties resultant from the diy spinning process, for a 44 dtex.
  • the term “degradable” is intended to include a composition that is susceptible to chemical breakdown. For example, a large molecule is degradable if it is prone to be broken into smaller molecules. Degradation may occur through any known process such as composting (including industrial composting), chemical degradation, biodegradation, marine degradation, and anaerobic digestion, as well as others.
  • biodegradable as used herein, it is meant a material which meets the test standard ASTM D5338, in terms of the aerobic biodegradation under controlled conditions.
  • high retractive force as used herein, it is meant a 5TM2 value greater than 1.2 cN for a 44 dtex fiber produced via dry spinning.
  • enzyme by “enzymatically biodegradable” it is meant a molecular weight loss % of at least 10% over a 4-week exposure to esterase enzyme.
  • compositions with a range of segmented polyurethanes or poly(urethane ureas) with engineered soft segment structure produced by incorporating a variable extent of polyester glycol into the capping process.
  • polyester glycol incoiporated into the polymer backbone ester linkages are positioned in the polymer backbone with certain structure to introduce weak points for the degradation reaction.
  • Elastic polyurethanes such as spandex or elastane (which terms are used herein interchangeably), include at least 85% of the fiber-forming substances as segmented polyurethanes or poly(urethane ureas) which include alternating soft segments and hard segments along the polymer chains.
  • segmented polyurethanes or poly(urethane ureas) which include alternating soft segments and hard segments along the polymer chains.
  • the spandex fiber properties are strongly dependent on the chemical structures and the segmental lengths (or molecular weights) of both the soft segment and the hard segment of the polymer, in addition to the unique structure or sequence of soft segments.
  • a glycol also referred to herein as a polyol, which are diols of polyethers, polyesters or polycarbonates, including their copolymers or mixtures is reacted with a diisocyanate in excess amount to form an isocyanate- terminated polyurethane or poly(urethane urea) prepolymer.
  • This prepolymer is then diluted in a solvent and chain extended with a short chain diol or diamine to grow the polymer chain length.
  • a terminator can be used to control the molecular weight of the polymer.
  • the soft segment is formed during the prepolymer formation stage and the hai’d segment is formed during the chain extension stage.
  • the formed polymer chains consist only of alternating soft segments and hard segments, each of a fixed chemical composition of a single glycol or diamine blend.
  • polyester-based glycols such as a copolymer of ethanediol, butanediol, and adipic acid, hereinafter referred to as “2G/4G-6”, into the capping or chain extension process, introduces a variable soft segment sequence, whereby the resultant polymer may consist of alternating segments of polyester and polyether functionality.
  • a polymer composition including segmented polyurethanes or poly(urethane ureas) according to the present invention based on glycols with molecular weight of 450 to 3300, preferably having a polyester composition of at least 25%, and an NCO of at least 1.8%, in order to appropriately balance polymer properties with resultant article structural properties.
  • the present invention also provides polymers produced by a blend ratio of poly ether to polyester glycol, through glycol blending, capped glycol blending, or polymer solution blending.
  • the present invention also provides fibers comprising the polymer composition of the present invention as well as articles of manufacture at least a portion of which comprises a fiber based on the compositions described herein.
  • Nonlimiting examples of such articles of manufacture of the present invention include fabrics and garments.
  • the fabrics and garments are for apparel and/or hygiene applications.
  • the article may include an elasticized laminate comprising at least a first layer and a second layer independently selected from the group consisting of a non-woven layer, a film, and combinations thereof. Where the article is an elasticized non-woven laminate the fiber is adjacent to or incorporated into the laminate.
  • the article may include a disposable hygiene product, disposable diaper, training pant or adult incontinence device or product; a catamenial device, garments or product; a bandage, wound dressing, surgical drape, surgical gown, surgical or other hygienic protective mask, hygienic gloves, head covering, head band, ostomy bag, bed pad or bed sheet.
  • composition of some embodiments may include a form selected from the group consisting of a dispersion, a solution, film, extrudate, and a fiber.
  • the polymer compositions are useful in producing spandex with high retractive force, low hysteresis, and enhanced susceptibility to biodegradation.
  • the spandex fibers are spun from the polymer compositions.
  • Spandex fibers may be, for example, but not limited to, dry spun, wet spun or melt spun. In one nonlimiting embodiment, the spandex fibers are dry spun.
  • the manufacturing of the polyurethane can occur either via batch polymerization or through the use of a continuous polymerization reactor.
  • Nonlimiting examples of diisocyanates useful in the present invention include 4,4’- methylene bisfphenyl isocyanate) (also referred to as 4,4-diphenylmethane diisocyanate (MDI)), 2,4’- methylene bis(phenyl isocyanate, 4,4’-methylenebis(cyclohexyl isocyanate), 1,4- xylenediisocyanate, 1 ,4-bis(isocyanatomethyl)cyclohexane, 2,6-toluenediisocyanate, 2,4- toluenediisocyanate, and mixtures thereof.
  • 4,4’- methylene bisfphenyl isocyanate) also referred to as 4,4-diphenylmethane diisocyanate (MDI)
  • 2,4’- methylene bis(phenyl isocyanate also referred to as 4,4-diphenylmethane diisocyanate (MDI)
  • Examples of specific diisocyanates include Takenate® 500 and FORTIMO® 1 ,4-H6XDl (Mitsui Chemicals), Mondur® MB (Bayer), Lupranate® M (BASF), and Isonate® 125 MDR (Dow Chemical), and combinations thereof.
  • the glycol or polyol component may include two or more glycols and must include at least 50% by weight of a polyester glycol.
  • a blend may include greater than 50% to 100% by weight polyester glycol. This includes blends that have greater than 60% by weight of a polyester, greater than 75% by weight polyester glycol or greater than 90% by weight polyester glycol.
  • the polyester glycol may have a number average molecular weight of about 450 to about 3300. This could include molecular weights of about 1000 to about 3000. The molecular weight may also be less than 2500, such as 500 to about 2500, or about 1000 to about 2000.
  • This polyester glycol can be combined with one or more other glycols, which may be either a polyester glycol, a polyether glycol or a polycarbonate glycol.
  • the additional glycol or glycols may have a number average molecular weight of about 400 to about 4000.
  • Examples of useful glycols include polyether glycols such as poly(tetramethylene ether) glycols (PTMEG), copolyether glycols such as poly(tetramethyleneether-co-ethyleneether) glycol and poly(tetramethylene ether-co-2 -methyltetramethylene ether) glycol, polyester and copolyester glycols such as polycaprolactone diol and those produced by condensation polymerization of aliphatic dicarboxylic acids and diols, or their mixtures, of low molecular weights with no-more than 12 carbon atoms in each molecule, and polycarbonate glycols produced by condensation polymerization of aliphatic diols with phosgene, dialkylcarbonates or diarylcarbonates.
  • PTMEG poly(tetramethylene ether) glycols
  • copolyether glycols such as poly(tetramethyleneether-co-ethyleneether) glycol and poly(tetramethylene ether-co-2
  • polyester glycols include poly(2,2-dimethyl- 1 ,3-propane) diol, neopentyl glycol, poly(2,2-dimethyl-l,3-propane dodecanedioate) glycol, poly(ethylene-co- 1 ,2-propylene adipate) glycol, poly(hexamethylene-co-2,2-dimethyltrimethylene adipate) glycol, and poly(ethylene-co-butylene adipate) glycol.
  • glycols examples include PTG-L glycols (Hodogaya Chemical Co., Ltd., Tokyo, Japan), ETERNACOLL® diols (Ube Industries, Ltd., Tokyo, Japan) and STEPANPOL® polyols (Stepan, Illinois, USA).
  • polyester polyols examples include, but are not limited to, those ester glycols with two or more hydroxy groups, produced by condensation polymerization of aliphatic polycarboxylic acids and polyols, or their mixtures, of low molecular weights with no more than 12 carbon atoms in each molecule.
  • suitable polycarboxylic acids include, but are not limited to, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, thiodibutyric acid, sulfonyldibutyric undecanedicarboxylic acid, and dodecanedicarboxylic acid.
  • polyester polyols examples include, but are not limited to, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, neopentyl glycol, 3- methyl -1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9- nonanediol, 1,10-decanediol and 1,12-dodecanediol.
  • a linear bifunctional polyester polyol with a melting temperature of about 5°C to 50°C is an example of a specific polyester polyol .
  • suitable polyols include, diethylene glycol, propane- 1,2-diol, butane- 1,3-diol, butane- 1,4-diol, hexane- 1,6-diol, hexahydro-p-xylyleneglycol, 2,2-dimethylpropane- 1 ,3-diol, 2, 2-diethylpropane-l ,3-diol, the hydroxyalkylation products of the above glycols and the like.
  • Polyesters of lactones, e.g. e- caprolactone may also be used as starting materials. Copolyesters may also be included.
  • the glycol component that includes a blend of two or more glycols may include a blend of polyftetramethyl ether) glycol and a polyester glycol or a copolyether glycol and a polyester glycol.
  • examples of polyether glycols that can be used include, but are not limited to, those glycols with two or more hydroxy groups, from ring-opening polymerization and/or copolymerization of ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and 3 -methyltetrahydrofuran, or from condensation polymerization of a polyhydric alcohol, such as a diol or diol mixtures, with less than 12 carbon atoms in each molecule, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, 2, 2-dimethyl-l, 3 propanediol, 3-methyl -1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10- de
  • Co-polymers can include poly(tetramethylene-co- ethyleneether) glycol.
  • examples of polycarbonate polyols that can be used include, but are not limited to, those carbonate glycols with two or more hydroxy groups, produced by condensation polymerization of phosgene, chloroformic acid ester, dialkyl carbonate or diallyl carbonate and aliphatic polyols, or their mixtures, of low molecular weights with no more than 12 carbon atoms in each molecule.
  • suitable polyols for preparing the polycarbonate polyols include, but are not limited to, diethylene glycol, 1,3-propanediol, 1 ,4-butanediol, 1,5- pentanediol, 1 ,6-hexanediol, neopentyl glycol, 3-methyl -1,5-pentanediol, 1,7-heptanediol, 1,8- octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol.
  • a linear, bifunctional polycarbonate polyol with a melting temperature of about 5°C to about 50°C is an example of a specific polycarbonate polyol.
  • Nonlimiting examples of diamine chain extenders useful in making the segmented polyfurethane urea)s according to the present invention include one or more diamines selected from 1 ,2-ethylenediamine; 1 ,4-butanediamine; 1 ,2-butanediamine; 1,3-butanediamine; 1,3- diamino-2,2-dimethylbutane; 1 ,6-hexamethylenediamine; 1,12-dodecanediamine; 1,2- propanediamine; 1 ,3-propanediamine ; 2-methyl-l,5-pentanediamine; 1 -amino-3 ,3 ,5-trimethyl-5- aminomethylcyclohexane; 2,4-diamino-l-methylcyclohexane; N-methylamino-bis(3- propylamine); 1,2-cyclohexanediamine; 1,4-cyclohexanediamine; 4,4’-methylene-bis (cyclohexylamine); isophorone di
  • the chain extender is a diol.
  • diols that may be used include, but are not limited to, ethylene glycol, 1,3- propanediol, 1,2-propylene glycol, 3 -methyl- 1,5-pentanediol, 2,2-dimethyl-l,3-trimethylene diol, 2,2,4-trimethyl- 1 ,5-pentanediol, 2-methyl-2-ethyl- 1 ,3-propanediol, 1 ,4- bis(hydroxyethoxy)benzene, and 1 ,4-butanediol and mixtures thereof.
  • Nonlimiting examples of useful chain terminators for the present invention include one or more monofunctional amines selected from ethylamine, propylamine, isopropylamine, n- butylamine, sec-butylamine, tert-butylamine, isobutylamine, isopentylamine, 1 -hexylamine, 1- octylamine, 2-ethyl-l -hexaneamine, cyclohexylamine, N,N-diethylamine, N-ethyl-N- propylamine, N,N-diisopropylamine, N-tert-butyl-N-methylamine, N-tert-butyl-N-benzylamine, N,N-dicyclohexylamine, N-ethyl-N-isopropylamine, N-tertbutyl-N-isopropylamine, N- isopropyl-N-cyclohexylamine,
  • a nonlimiting example of the solvent used in the present invention is N,N- dimethylacetamide (DMAc).
  • DMAc N,N- dimethylacetamide
  • Other solvents suitable for polyurethane and/or polyurethaneurea may be included.
  • Classes of additives that may be optionally included in polyurethane and poly(urethane urea) compositions are listed below.
  • An exemplary and non-limiting list include: anti-oxidants, UV stabilizers, colorants, pigments, cross-linking agents, phase change materials (paraffin wax), antimicrobials, minerals (e.g., copper), microencapsulated additives (e.g., aloe vera, vitamin E gel, aloe vera, sea kelp, nicotine, caffeine, scents or aromas), nanoparticles (e.g., silica or carbon), nano-clay, calcium carbonate, talc, flame retardants, antitack additives, chlorine degradation resistant additives, vitamins, medicines, fragrances, electrically conductive additives, dyeability and/or dye-assist agents (such as quaternary ammonium salts).
  • additives which may be added to the poly( urethane urea) compositions include adhesion promoters, anti-static agents, anti-creep agents, optical brighteners, coalescing agents, electroconductive additives, luminescent additives, lubricants, organic and inorganic fillers, preservatives, texturizing agents, thermochromic additives, insect repellants, and wetting agents, stabilizers (hindered phenols, zinc oxide, hindered amine), slip agents (silicone oil) and combinations thereof.
  • An additive may also include a degradability enhancing additive or degradability retarding additive. Additives that enhance degradability are described herein in further detail.
  • the additive may provide one or more beneficial properties including: dyeability, hydrophobicity (e.g., polytetrafluoroethylene (PTFE)), hydrophilicity (e.g., cellulose), friction control, chlorine resistance, degradation resistance (e.g., antioxidants), adhesiveness and/or fusibility (e.g., adhesives and adhesion promoters), flame retardance, antimicrobial behavior (silver, copper, ammonium salt), barrier, electrical conductivity (carbon black), tensile properties, color, luminescence, recyclability, biodegradability, fragrance, tack control (e.g., metal stearates), tactile properties, set-ability, thermal regulation (e.g., phase change materials), nutriceutical, delustrant such as titanium dioxide, stabilizers such as hydrotalcite, a mixture of huntite and hydromagnesite, UV screeners, and combinations thereof.
  • beneficial properties including: dyeability, hydrophobicity (e.g., polytetrafluoroethylene (PTFE)
  • a degradability enhancing additive may be selected from the group consisting of cellulose esters (cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate), soluble cellulosics (methyl cellulose, ethyl cellulose, hydroxypropyl methylcellulose), insoluble cellulosics (microcrystalline cellulose, nanocrystalline cellulose, cellulose fibrils), polyvinyl alcohol, cetyl alcohol, and starches.
  • Any of the compositions, fibers, and/or articles may include one or more degradability enhancing additive.
  • Suitable amounst of the degradability enhancing additive may be in an amount of up to about 5%. Depending on the desired level of degradability the amount may be .01% to about 5% by weight of the composition, about 1% to about 5% or about 1% to about 2%.
  • the linear density of the yams useful in some aspects can range from about 15 denier (D) (16.5 dtex) to about 450 denier, including about 15 denier to about 300 denier (330 dtex), including from about 30 denier to 100 denier (33 dtex to 110 dtex) for apparel uses. Heavier denier such as greater than 450 denier, may be useful to achieve other properties. Historically, higher deniers such as 500-1200 denier may be preferred for hygiene end use.
  • nonwoven or “nonwoven material” refers herein to a material made from continuous (long) filaments (fibers) and/or discontinuous (short) filaments (fibers) by processes such as spunbonding, meltblowing, carding, and the like. Nonwovens do not have a woven or knitted filament pattern
  • nonwoven web means a manufactured sheet, web, or batt of directionally or randomly orientated fibers, bonded by friction, and/or cohesion, and/or adhesion, excluding paper and products which are woven, knitted, tufted, stitch-bonded incorporating binding yarns or filaments, or felted by wet-milling, whether or not additionally needled.
  • the fibers may be of natural or man-made origin and may be staple or continuous filaments or be formed in situ.
  • Nonwoven webs may be formed by many processes such as meltblowing, spunbonding, solvent spinning, electrospinning, carding, and airlaying. The basis weight of nonwoven webs is usually expressed in grams per square meter (g/m2 or gsm).
  • joind encompasses configurations whereby an element is directly secured to another element by affixing the element directly to the other element, and configurations whereby an element is indirectly secured to another element by affixing the element to intermediate member(s) which in turn are affixed to the other element.
  • the process steps involved in making the segmented polyurethanes or poly(urethane ureas) of the present invention can be a batch process or a continuous process or their combinations.
  • individual glycols undergo capping by batch processes, which are then combined in capped glycol form in a set ratio, in order to make the polymer with chain extension and termination in a solvent by a continuous polymerization process.
  • the steps involved in glycol capping with a diisocyanate are performed with heat, with or without the use of a catalyst, typically in a temperature range of 50 to 100°C.
  • glycols can be subjected to the capping reaction with two or more isocyanates, where each glycol utilized in the polyurethane or poly(urethane urea) polymer is capped wdth a different type of diisocyanate.
  • the biodegradable polyurethane or poly(urethane urea) elastic fiber is spun from a solution-polymerized polyurethane polymer solution by a prepolymer method.
  • the biodegradable polyurethane or poly(urethane urea) elastic fiber is used to elasticize a nonwoven laminate.
  • the biodegradable polyurethane or poly(urethane urea) elastic fiber may be encompassed within or juxtaposed with the nonwoven laminate.
  • biodegradable polyurethane or poly(urethane urea) elastic fiber is first elongated and then applied or incorporated within the nonwoven laminate in its elongated state.
  • this process of producing spandex polymers based on polyester or polyether glycol blends is useful in the production of segmented polyurethanes or poly(urethane ureas) with biodegradation rates and tensile properties.
  • Percent isocyanate (%NCO) of the capped glycol prepolymer was determined according to the method of S. Siggia. “Quantitative Organic Analysis via Functional Group”, 3rd Edition, Wiley & Sons, New York, pages 559-561 (1963) using a potentiometric titration.
  • %SD - (5LP300 - 5UP300) x 100/5LP300 Where 5LP3OO and 5UP300 in centinewtons are respectively the load power and unload power at 300% extension of the sample. Percent set was also measured on samples that had been subjected to five 0 - 300% elongation/relaxation cycles. The percent set, %SET, was then calculated as - %SET - 100 x (Lf - Lo)/Lo where Lo and Lf are respectively the filament (yarn) length when held straight without tension before and after the five elongation/relaxation cycles.
  • MW Molecular weight
  • Degradation properties were assessed by means of an accelerated degradation test, utilizing exposure of yam to a purified enzyme.
  • Esterase enzyme from porcine liver, was utilized at > 15 units enzyme activity, which the standardized activity necessary to hydrolyze 1 .0 micromole of ethyl butyrate to butyric acid and ethanol per minute at pH 8.0 at 25°C.
  • Samples of 50 mg of yam were treated with 10 mg of esterase in 2 mL of phosphate buffered saline (PBS) at pH 7.4 for 4 weeks. At each week interval, enzyme solution was removed and replaced, and samples collected for mass and molecular weight determination.
  • PBS phosphate buffered saline
  • Mass Loss (%) (ME 0 - ME 4 )/ME U
  • PTMEG 1800 is a poly(tetramethylene ether) glycol, with a number average molecular weight of 1800 grams/mole, supplied by Dairen.
  • 2G/4G-6 is a polyester glycol (hexanedioic acid, polymer with 1,4-butanediol and 1,2- ethanediol), with an average number molecular weight of 1500 grams/mole.
  • Isonate® 125MDR or MDI is a mixture of diphenylmethane diisocyanate containing 98% 4,4’-MDI isomer and 2% 2,4’-MDI isomer (commercially available from the Dow Company, Midland, Michigan).
  • EDA stands for ethylenediamine as a chain extender
  • DEA stands for N,N-diethylamine as the chain terminator
  • DMAc stands for N,N-dimethylacetamide as the solvent.
  • Example 1 A prepolymer was obtained by reacting a polyester glycol (hexanedioic acid, polymer with 1 ,4-butanediol and 1 ,2-ethanediol) with a molecular weight of 1485 g/mole with 200 ppm 85% phosphoric acid and 4,4'-diphenylmethane diisocyanate (MDI) at a 3.75:1.00 (weight by weight), respectively, in a batch polymerization process under neat conditions at 90°C for 120 min at a specified reaction rate.
  • MDI 4,4'-diphenylmethane diisocyanate
  • the residual isocyanate group after the reaction was targeted as 2.60 weight %.
  • the capping ratio (mole ratio of isocyanate to glycol) was 1.58. 348.31 grams of the obtained prepolymer were dissolved in 613.55 grams of DM Ac at 60°C, and the chain extender solution in which 6.44 grams of ethylenediamine
  • a prepolymer was obtained by reacting a polyester glycol (hexanedioic acid, polymer with 1 ,4-butanediol and 1 ,2-ethanediol) with a molecular weight of 987 g/mole with 200 ppm 85% phosphoric acid and 4,4'-diphenylmethane diisocyanate (MDI) at a 2.79: 1.00 (weight by weight), respectively, in a batch polymerization process under neat conditions at 90°C for 60 min at a specified reaction rate.
  • MDI 4,4'-diphenylmethane diisocyanate
  • the residual isocyanate group after the reaction was targeted as 2.60 weight %.
  • the capping ratio (mole ratio of isocyanate to glycol) was 1.42.
  • a prepolymer was obtained by reacting a polyester glycol (hexanedioic acid, polymer with 1 ,4-butanediol and 1 ,2-ethanediol) with a molecular weight of 2,056 g/mole with 200 ppm 85% phosphoric acid and 4,4'-diphenylmethane diisocyanate (MDI) at a 4.63: 1.00 (weight by weight), respectively, in a batch polymerization process under neat conditions at 100°C for 60 min at a specified reaction rate.
  • MDI 4,4'-diphenylmethane diisocyanate
  • the residual isocyanate group after the reaction was targeted as 2.60 weight %.
  • the capping ratio (mole ratio of isocyanate to glycol) was 1.77.
  • a prepolymer was obtained by reacting a blend of 75 wt% polyester glycol (hexanedioic acid, polymer with 1,4-butanediol and 1,2-ethanediol) and 25 wt% poly(tetramethylene ether) glycol (PTMEG) with a molecular weight of 1 ,475 g/mole with 200 ppm 85% phosphoric acid and 4,4'-diphenylmethane diisocyanate (MDI) at a 3.73:1.00 (weight by weight), respectively, in a batch polymerization process under neat conditions at 100°C for 75 min at a specified reaction rate. The residual isocyanate group after the reaction was targeted as 2.60 weight %.
  • polyester glycol hexanedioic acid, polymer with 1,4-butanediol and 1,2-ethanediol
  • PTMEG poly(tetramethylene ether) glycol
  • MDI 4,4'-dip
  • the capping ratio (mole ratio of isocyanate to glycol) was 1.58. 348.65 grams of the obtained prepolymer were dissolved in 581.11 grams of DMAc at 60°C, and the chain extender solution in which 6.41 grams of ethylenediamine and 0.56 grams of diethylamine and 107.37 grams DMAc was added while stirring vigorously at 80°C to obtain a viscosity adjusted polymer solution of 34 weight % concentration.
  • a prepolymer was obtained by reacting a blend of 50 wt% polyester glycol (hexanedioic acid, polymer with 1 ,4-butanediol and 1 ,2-ethanediol) and 50 wt% poly(tetramethylene ether) glycol (PTMEG) with a molecular weight of 1,470 g/mole with 200 ppm 85% phosphoric acid and 4,4-diphenylmethane diisocyanate (MDI) at a 3.72:1.00 (weight by weight), respectively, in a batch polymerization process under neat conditions at 100°C for 75 min at a specified reaction rate.
  • MDI 4,4-diphenylmethane diisocyanate
  • the capping ratio (mole ratio of isocyanate to glycol) was 1.58. 350.09 grams of the obtained prepolymer were dissolved in 646.76 grams of DMAc at 60°C, and the chain extender solution in which 6.40 grams of ethylenediamine and 0.65 grams of diethylamine and 108.39 grams DMAc was added while stirring vigorously at 80°C to obtain a viscosity adjusted polymer solution of 32 weight % concentration.
  • a prepolymer was obtained by reacting a polyester glycol (hexanedioic acid, polymer with 1 ,4-butanediol and 1 ,2-ethanediol) with a molecular weight of 1 ,480 g/mole with 200 ppm 85% phosphoric acid and 4, 4' -diphenylmethane diisocyanate (MDI) at a 3.63: 1.00 (weight by weight), respectively, in a batch polymerization process under neat conditions at 100°C for 75 min at a specified reaction rate.
  • MDI 4' -diphenylmethane diisocyanate
  • the capping ratio (mole ratio of isocyanate to glycol) was 1.63. 350.75 grams of the obtained prepolymer were dissolved in 609.94 grams of DMAc at 60°C, and the chain extender solution in which 6.92 grams of ethylenediamine and 0.65 grams of diethylamine and
  • a prepolymer was obtained by reacting a polyester glycol (hexanedioic acid, polymer with 1 ,4-butanediol and 1 ,2-ethanediol) with a molecular weight of 1 ,480 g/mole with 200 ppm 85% phosphoric acid and 4,4'-diphenylmethane diisocyanate (MDI) at a 3.98: 1.00 (weight by weight), respectively, in a batch polymerization process under neat conditions at 100°C for 75 min at a specified reaction rate.
  • MDI 4,4'-diphenylmethane diisocyanate
  • the residual isocyanate group after the reaction was targeted as 2.20 weight %.
  • the capping ratio (mole ratio of isocyanate to glycol) was 1.48.
  • a prepolymer was obtained by reacting a polyester glycol (hexanedioic acid, polymer with 1 ,4-butanediol and 1 ,2-ethanediol) with a molecular weight of 1,480 g/mole with 200 ppm 85% phosphoric acid and 4,4 -diphenylmethane diisocyanate (MDI) at a 3.74:1.00 (weight by weight), respectively, in a batch polymerization process under neat conditions at 100°C for 75 min at a specified reaction rate.
  • MDI 4,4 -diphenylmethane diisocyanate
  • the residual isocyanate group after the reaction was targeted as 2.60 weight %.
  • the capping ratio (mole ratio of isocyanate to glycol) was 1.58.
  • a prepolymer was obtained by reacting a polyester glycol (hexanedioic acid, polymer with 1,4-butanediol and 1,2-ethanediol) with a molecular weight of 2,968 g/mole with 200 ppm 85% phosphoric acid and 4,4'-diphenylmethane diisocyanate (MDI) at a 6.54: 1.00 (weight by weight), respectively, in a batch polymerization process under neat conditions at 100°C for 120 min at a specified reaction rate.
  • MDI 4,4'-diphenylmethane diisocyanate
  • the residual isocyanate group after the reaction was targeted as 2.00 weight %.
  • the capping ratio (mole ratio of isocyanate to glycol) was 1.81.
  • degradability enhancing additives were included with the polyester glycol-based polyurethanes. These result in an enhancement of degradability Testing for degradation was under ASTM D6400 which measures disintegration by sieving the compost- plastic mixture after a set time to measure the amount of material passage through the sieve.
  • This application can be used in any form that the polymer may be made into, e.g. films, fibers, solution castings.
  • One or more additives are incorporated via a slurry process then mixed into the polymer solution to be formed. These additives may be in the range of 0.1% to 50% on weight of the polymer substrate. Not only do the additives themselves degrade, but also in turn provide augmented degradation of the polymer.
  • the benefits imparted by the additives include sustainable material use, inherent additive biodegradation, changing of the polymer hydrophilicity, or even attracting more microbial activity to the surface of the base polyester.
  • DMAc Dimethylacetamide
  • Degradability enhancing additives include cellulosics such as cellulose acetate, cellulose propionate, cellulose butyrate, alkyl cellulose, hypromellose, starches, micro/nano-crystalline cellulose, cellulose fibrils, alginates, and fatty alcohols (e.g. hexadecanol), polyvinyl pyrrolidone. Various molecular weights/viscosities were investigated.
  • Other additives that are used in processing are antioxidants such as Irganox 245, Irganox 1019, Irganox 1076, Irganox 1098, and silicone spinning aids such as Dimethicone 10 cS and 100 cS.
  • the slurry of additives is mixed with overhead agitators equipped with a turbine blade and rotor stator mixers. Additions of the slurry into the final polymer is also mixed with overhead mixers and flat disc bl ades. If particle size reduction is needed, then media mills with 0.8-1.0 mm ceramic beads were utilized.
  • Compost inoculum was procured from a local facility that participated in the US Composting Council’s Seal of Testing Assurance Program.
  • the degree of disintegration, Dis% is calculated in % using the following: where is the initial dry mass of polymer to be incubated is the final dry mass of polymer to remaining on the 2 mm screen
  • Molecular weights (Mn and Mw) were analyzed using gel permeation chromatography (GPC) on an Agilent 1 100 series analyzer equipped with a diode array detector. Polystyrene standards were ran as calibration. The number and weight averages were measured on the un- composted and composted samples. Similar calculations of degradation, , can be performed to bio-disintegration: where is the initial n (number) or w (weight) molecular averages of polymer is the final n (number) or w (weight) molecular averages of polymer after composting Base Slurry
  • a base slurry solution is prepared by mixing 263.29 g of DMAc, 165.28 g of Irganox 245, 66.14 g of 10 cS polydimethylsiloxane, and 255.29 g of a 35% polyether-urethane polymer solution. This will be used in each formulation of a standard antioxidant and spinning aid additive package.
  • Soluble additives that provide sufficient viscosity when dissolved in DMAc were made as follows (wt %): 25% cellulose acetate (CA, grade ‘CAI ’), 12.5% cellulose acetate (CA, grade ‘CA2’), 30% cellulose acetate propionate (CAP, ‘CAP1’) 482-0.5, 15% cellulose acetate propionate (CAP, ‘CAP2’), and 35% cellulose acetate butyrate (CAB, ‘CAB1’).
  • Cellulose acetate composition is 40% acetyl content, 3.5% hydroxyl content, and viscosity ranging from 10-200 Poise.
  • Cellulose acetate propionate composition is 1-2% acetyl content, 40-50% propionyl, 1-3% hydroxyl content, and ranged from 1-100 Poise viscosity.
  • Cellulose acetate butyrate content is 2% acetyl content, 50-54% butyryl content, up to 2% hydroxyl content, and viscosity ranging from 0-2 Poise.
  • Polymer films were then prepared using the above slurry formulations: Table A. Compositions of polymers with biodegrading enhancing additives at a 2% (wt/wt) level.
  • additive Slurry (g) additive Slurry (g)

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Abstract

L'invention concerne une composition de polyuréthane-urée dégradable qui peut être une fibre comprenant un glycol, un diisocyanate et un allongeur de chaîne; le composant glycol comprenant plus de 50% en poids d'un polyester glycol ayant un poids moléculaire moyen en nombre d'environ 450 à environ 3300 et la fibre étant dégradable.
PCT/US2023/083707 2022-12-12 2023-12-12 Composition de polyuréthane élastique dégradable WO2024129790A2 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8357767B2 (en) 2007-10-03 2013-01-22 Polynovo Biomaterials Limited High modulus polyurethane and polyurethane/urea compositions
CN109338504A (zh) 2018-09-17 2019-02-15 浙江华峰氨纶股份有限公司 一种生物易降解氨纶用高性能聚氨酯及其制备方法

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US3994881A (en) * 1975-07-24 1976-11-30 E. I. Du Pont De Nemours And Company Spandex process and product based on tetra-halogenated diisocyanates and diamines

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8357767B2 (en) 2007-10-03 2013-01-22 Polynovo Biomaterials Limited High modulus polyurethane and polyurethane/urea compositions
CN109338504A (zh) 2018-09-17 2019-02-15 浙江华峰氨纶股份有限公司 一种生物易降解氨纶用高性能聚氨酯及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
S. SIGGIA.: "Quantitative Organic Analysis via Functional Group", 1963, WILEY & SONS, pages: 559 - 561

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