WO2005092948A2 - Anaerobically biodegradable polyesters - Google Patents
Anaerobically biodegradable polyesters Download PDFInfo
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- WO2005092948A2 WO2005092948A2 PCT/US2005/008214 US2005008214W WO2005092948A2 WO 2005092948 A2 WO2005092948 A2 WO 2005092948A2 US 2005008214 W US2005008214 W US 2005008214W WO 2005092948 A2 WO2005092948 A2 WO 2005092948A2
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/51—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the outer layers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/15203—Properties of the article, e.g. stiffness or absorbency
- A61F13/15252—Properties of the article, e.g. stiffness or absorbency compostable or biodegradable
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/51—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the outer layers
- A61F13/514—Backsheet, i.e. the impermeable cover or layer furthest from the skin
- A61F13/51401—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by the material
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/62—Compostable, hydrosoluble or hydrodegradable materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0033—Additives activating the degradation of the macromolecular compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
Definitions
- This invention generally relates to anaerobically biodegradable polyesters.
- the invention also relates to compositions and articles of manufacture containing or made from the polyesters.
- Particularly useful articles include films, fibers, non-woven fabrics, and adhesives. These articles can be used to make other anaerobically biodegradable end-use articles such as diapers, feminine-hygiene products, and incontinence briefs.
- thermoplastic polymers such as polypropylene and polyesters.
- These films, fibers, and fibrous articles are commonly used in non- woven fabrics and composite structures containing continuous films and, in particular, personal care products such as wipes, feminine and personal hygiene products, baby diapers, adult incontinence briefs, hospital/surgical and other medical disposables, protective fabrics and layers, geotextiles, and filter media.
- personal care products made from conventional thermoplastic polymers are difficult to dispose of and are usually placed in landfills or composting facilities.
- Flushability has traditionally been focused on compatibility with domestic and municipal plumbing fixtures, and has been defined as the ability to reduce the bulk of the product to be disposed by the consumer in an aqueous environment (e.g., dispersible upon contact with water in a toilet or industrial hot-water treatment).
- aqueous environment e.g., dispersible upon contact with water in a toilet or industrial hot-water treatment.
- Various approaches to addressing these needs have been described, for example, in U.S. Patent Nos. 6,548,592; 6,552,162; 5,281,306; 5,292,581; 5,935,880; and 5,509,913, U.S. Patent Application Nos. 09/775,312 and 09/752,017, and PCT International Publication No. WO 01/66666 A2.
- polyesteramides, polyhydroxyalkoates, and mixtures thereof are anaerobically degradable.
- Comparative Examples 4a and 4b the publication notes that aliphatic polyester BionoUe 3001 and aliphatic-aromatic copolyester Eastar 14766 "do not provide satisfactory degradability in an anaerobic sludge.”
- polymers, particularly aliphatic- aromatic copolyesters, and articles made therefrom that can biodegrade under partially or completely anaerobic conditions.
- the invention relates to aliphatic-aromatic polyesters that comprise aromatic monomers in an amount effective to render them anaerobically biodegradable, hi one embodiment, the anaerobically biodegradable polyesters comprise: (a) diacid residues comprising from about 39 to about 43 mole percent of residues from an aromatic dicarboxylic acid and from about 57 to about 61 mole percent of residues from a non-aromatic dicarboxylic acid; and (b) diol residues comprising from about 85 to about 100 mole percent of residues from 1,4-butanediol and from about 0 to about 15 mole percent of residues from another diol.
- the polyesters comprise: (a) diacid residues comprising from about 39 to about 43 mole percent of residues from terephthalic acid and from about 57 to about 61 mole percent of residues from adipic acid or glutaric acid; and (b) diol residues comprising about 100 mole percent of residues from 1,4-butanediol.
- the invention relates to compositions comprising the anaerobically biodegradable polyesters and a thermoplastic starch, inorganic . salt, or both.
- the invention relates to articles of manufacture made from or containing the anaerobically biodegradable polyesters and compositions of the invention. Such articles include films, fibers, non-woven fabrics, and adhesives. The polyesters and compositions are particularly useful in absorbent articles and tampon applicator assemblies.
- Aliphatic-aromatic polyesters are known to be biodegradable under aerobic conditions. But when these materials are exposed to the anaerobic conditions typical of the septic or sewage system, they generally fail to degrade. significantly within a reasonable amount of time. See, e.g., US 2002/0042599 Al at paras. 0003 and 0091. We have surprisingly and unexpectedly discovered, however, that ahphatic-aromatic polyesters can be made anaerobically biodegradable by limiting the amount of aromatic monomers in the polyester. As used herein, the indefinite article "a" means one or more.
- a range stated to be 0 to 10 is intended to disclose all whole numbers between 0 and 10 such as, " for example 1, 2, 3, 4, etc., all fractional numbers between 0v. and 10, for example 1.5, 2.3, 4.57, 6.1113, etc., and the endpoints 0 and 10..
- the numerical ranges and parameters describing the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
- polyyester as used herein, is intended to include
- polyesters are synthetic polymers prepared by the polycondensation of one or more difunctional carboxylic acids with one or more difunctional hydroxyl compounds.
- the difunctional carboxylic acid is a dicarboxylic acid
- the difunctional hydroxyl compound is a dihydric alcohol such as, for example, glycols and diols.
- the polyester may optionally be modified with one or more hydroxycarboxylic acids (or their polyester-forming derivatives).
- polyesters can be formed via a ring opening reaction of cyclic lactones; for example, as in polylactic acid prepared from its cyclic lactide or polycaprolactone formed from caprolactone.
- aliphatic-aromatic polyester means a polyester comprising a mixture of residues from aliphatic or cycloahphatic dicarboxylic acids or diols and aromatic dicarboxylic acids or diols.
- aromatic means the dicarboxylic acid or diol contains an aromatic nucleus in the backbone such as, for example, terephthalic acid or 2,6-naphthalene dicarboxylic acid.
- non-aromatic as used herein with respect to the dicarboxylic acid, diol, and hydroxycarboxylic acid monomers, means that carboxyl or hydroxyl groups of the monomer are not connected through an aromatic nucleus.
- adipic acid contains no aromatic nucleus in its backbone, i.e., the chain of carbon atoms connecting the carboxylic acid groups; thus, it is "non-aromatic".
- Non-aromatic is intended to include both aliphatic and cycloahphatic structures such as, for example, diols, diacids, and hydroxycarboxylic acids, that contain as a backbone a straight or branched chain or cyclic arrangement of the constituent carbon atoms which may be saturated or paraffmic in nature, unsaturated (i.e., containing non-aromatic carbon-carbon double bonds), or acetylenic (i.e., containing carbon-carbon triple bonds).
- non-aromatic is intended to include linear and branched, chain structures (referred to herein as “aliphatic”) and cyclic structures (referred to herein as “alicyclic” or “cycloaliphatic”).
- aliphatic chain structures
- cyclic cycloaliphatic
- non- aromatic is not intended to exclude any aromatic substituents that may be attached to the backbone of an aliphatic or cycloaliphatic diol or diacid or hydroxycarboxylic acid.
- the difunctional carboxylic acid may be an aliphatic or cycloaliphatic dicarboxylic acid such as, for example, adipic acid, or an aromatic dicarboxylic acid such as, for example, terephthalic acid.
- the difunctional hydroxyl compound may be cycloaliphatic diol such as, for example, 1,4-cyclohexanedimethanol, a linear or branched aliphatic diol such as, for example, 1,4-butanediol, or an aromatic diol such as, for example, hydroquinone.
- the term “residue”, as used herein, means any organic structure incorporated into a polymer through a polycondensation reaction involving the corresponding monomer.
- the term “repeating unit”, as used herein, means an organic structure having a dicarboxylic acid residue and a diol residue or hydroxycarboxyhc acid residues bonded through a carbonyloxy group.
- the dicarboxylic acid residues maybe derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof.
- dicarboxylic acid is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, mcluding its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a polycondensation process with a diol to make a high molecular weight polyester.
- hydroxycarboxylic acid refers to monohydroxy- monocarboxylic acids including aliphatic and cycloaliphatic hydroxycarboxylic acids and any derivative thereof, including their associated acid halides, esters, cyclic esters (including dimers such as lactic acid lactides), salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a . polycondensation process or ring opening reaction to make a high molecular weight polyester.
- anaerobically biodegradable means the polyester, composition, or article (such as films, fibers, nonwovens, laminates, shaped articles, etc.) is capable of being at least partially degraded, weakened, broken into pieces, disintegrated, or dissolved, in an anaerobic or microaerophilic environment such as those encountered in an active sewage sludge obtained from a municipal waste water treatment plant or septic system within a reasonable amount of time, such as from 1 to 3 months. Whether materials undergo complete biodegradation has been debated in International Standards organizations, such as the ASTM, US Composting Council, CEN (Europe), DIN (Germany), and Asia.
- Microorganisms exhibit a wide range of tolerance to and differential requirements for oxygen. Even organisms considered strict anaerobes can metabolize oxygen when it is available, though they do not grow well in tha; presence of this gas. In biodegradable communities of microorganisms, a whole range of oxygen requirements are observed. Strictly speaking, the term "anaerobic" means without air (or more specifically, free oxygen), but almost no liquid biodegradation medium is completely without air. Thus, a better description of a septic tank or sewage environment would be microaerophilic (very small amount of air). Just the addition of new material with liquid into a septic tank or sewage system (by flushes) necessarily carries with it some dissolved oxygen.
- anaerobic is not used herein in its literal sense. It is used more broadly to mean partially or completely depleted of free oxygen, such as the microaerophilic environment typically encountered in a septic tank or sewage system. It is well documented that some compounds are metabolized only when oxygen is not present and that the available oxygen is depleted by aerobic and microaerophilic organisms. Examples are phenolic compounds and highly chlorinated molecules. The components of aliphatic-aromatic polyesters, such as EASTAR BIO copolyester, are not among these compounds. In a completely anaerobic environment, it has been observed that no biodegradation or even fragmentation of EASTAR BIO copolyester occurs.
- the anaerobically biodegradable polyesters of the present invention typically are prepared from dicarboxylic acids and diols, which react in substantially equal proportions, and are incorporated into the polyester polymer as their corresponding residues. They may optionally be prepared in the additional presence of hydroxycarboxylic acids or polyester-forming derivatives thereof.
- the polyesters derived from dicarboxylic acid and diol residues of the present invention therefore, contain substantially equal molar proportions of diacid residues (100 mole%) and diol residues (100 mole%) such that the total moles of repeating units is equal to 100 mole%.
- the polyesters can be modified by incorporating hydroxycarboxylic acids without affecting these 100 mole% totals (i.e., -hydroxycarboxylic acids do not enter into this 100 mole% counting since they already contain a stoichiometric balance between acid and hydroxy groups).
- the mole percentages of diacids in the present disclosure are expressed as a fraction (or percentage) of the total moles of diacid residues in any particular polymer sample.
- a copolyester containing 60 mole% adipic acid based on the total diacid residues, means that the copolyester contains 60 mole% adipic acid residues out of a total of 100 mole% diacid residues.
- the mole percentages of diols are expressed as a fraction (or percentage) of the total moles of diol residues in the polymer sample.
- a copolyester containing 15 mole% ethylene glycol based on the total diol residues, means that the copolyester contains 15 mole% of ethylene glycol residues out of a total of 100 mole% of diol residues.
- the mole percentages of hydroxycarboxyhc acids herein are expressed as a fraction (or percentage) of the total moles of diacid residues in the polymer sample.
- a polymer comprising of 10 mole% of a hydroxycarboxylic acid, 60 mole% of adipic acid, 40 mole% of terephthalic acid, and 100 mole% of butandiol means that there is one tenth the number of moles of hydroxycarboxylic acid residues in the sample as there are moles of diacid residues (in this case, moles of adipic acid residues plus moles of terephthalic acid residues) in the sample.
- the anaerobically biodegradable polyesters of the invention may comprise residues of one or more non-aromatic dicarboxylic acids.
- non-aromatic dicarboxylic acids include glutaric and adipic.
- the anaerobically biodegradable polyesters may comprise residues of aromatic dicarboxylic acids.
- aromatic dicarboxylic acids examples include terephthalic acid, isophthahc acid, 5-sulfoisophthalic acid, and 2,6- naphthalenedicarboxylic acid.
- the aromatic dicarboxylic acid comprises terephthalic acid with up to 5 mole% of the terephthalic acid being replaced with one or more of isophthahc acid, 5-sulfoisophthalic acid, and 2,6-naphthalenedicarboxylic acid.
- the aromatic dicarboxylic acid residues are present in the polyesters of the invention in an amount that is effective to render the polyesters biodegradable under anaerobic conditions.
- ahphatic-aromatic polyesters containing from about 39 to about; 43 mole% of aromatic dicarboxylic acid residues, based on the total moles of diacid residues in the polyester can be expected to be anaerobically biodegradable.
- Aliphatic-aromatic polyesters containing from about 40 to about 42 mole% of aromatic dicarboxylic acid residues, based on the total moles of diacid residues in the polyester can also be expected to be anaerobically biodegradable.
- additional aromatic dicarboxylic acid residue ranges that can be expected to yield anaerobically biodegradable polyester compositions include from about 39 to about 46 mole%, and from about 41 to about 43 mole%.
- diols examples include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 2,2-dimethyl-l,3-propanediol, 1,3- butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, polyethylene glycol, diethylene glycol, 2,2,4-trimethyl-l,6-hexanediol, thiodiethanol, 1,3- cyclohexanedimethanol, 1 ,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl- 1 ,3- cyclobutanediol, triethylene glycol, and tetraethylene glycol with the preferred diols comprising one or more diols selected from ethylene glycol, diethylene glycol, 1,3-propane
- the polyesters of the invention comprise from about 85 to about 100 mole% of residues from 1,4- butanediol and from about 0 to about 15 mole percent of residues from another diol.
- the polyesters comprise about 100 mole% of 1,4- butanediol residues .
- the anaerobically biodegradable polyesters of the instant invention can be readily prepared from the appropriate dicarboxylic acids, esters, anhydrides, or salts, the appropriate diol or diol mixtures, and any branching agents .using - : typical polycondensation reaction conditions. They may be made by continuous, semi-continuous, and batch modes of operation and may utilize a variety of reactor types.
- reactor types include, but are not limited to, stirred tank, continuous stirred tank, slurry, tubular, wiped-film, falling film, or extrusion reactors.
- the anaerobically biodegradable polyesters of the present invention can be prepared by procedures known to persons skilled in the art and described, for example, in U.S. Patent No. 2,012,267. Such reactions are usually carried out at temperatures from 150°C to 300°C in the presence of polycondensation catalysts such as, for example, alkoxy titanium compounds, alkali metal hydroxides and alcoholates, salts of organic carboxylic acids, alkyl tin compounds, metal oxides, and the like.
- the catalysts are typically employed in amounts between 10 to 1000 ppm, based on total weight of the reactants.
- the polyesters can be modified by incorporating up to about 15 mole% of hydroxycarboxylic acid residues, based on the total moles of diacid residues.
- the total mole% of (1) aliphatic diacid residues; (2) diol residues other than 1 ,4-butanediol residues, if any; and (3) hydroxycarboxylic acid residues, if any, is desirably less than about 65.
- the total mole% of (1) + (2) + (3) can range from about 50 to about 65, about 55 to about 62, or about 58 to about 62.
- Suitable hydroxycarboxylic acids include garnma- butyrolactone; caprolactone; lactic acid (D or L-form or mixtures thereof); aliphatic hydroxyalkylates including 4-hydroxybutanoic acid, 4-hydroxyvaleric acid, 4-hydroxyhexanoic acid, and 4-hydroxyoctanoic acid; and derivatives thereof useful for the production of polyesters.
- hydroxycarboxylic acids can be incorporated by direction reaction into the polyester through conventional means by reacting them in their free acid form or other polyester forming derivatives, for example their esters (including cyclic esters called lactones), or by reactive blending them with the above polyesters in their polymeric form such as polyhydroxyalkanoates (PHAs) such as polyhydroxybutyrate (PHB), polyhydroxybutyrate-co-valerate (PHBv), polyhydroxybutyrate-co-octanoate (PHBO), and polyhydroxybutyrate-co- hexanoate (PHBHx); polycaprolactone (PCL), and polylactic acid (PLA) from synthetic or natural sources.
- PHAs polyhydroxyalkanoates
- PBHx polyhydroxybutyrate
- PCL polycaprolactone
- PLA polylactic acid
- the anaerobically biodegradable polyesters can comprise from about 10 to about 1,000 repeating units. They can also comprise from about 15 to about 600 repeating units.
- the anaerobically biodegradable polyesters can have an inherent viscosity of about 0.4 to about 2.0 dL/g, or about 0.7 to about 1.4, as measured at a temperature of 25°C using a concentration of 0.5 gram polyester in 100 ml of a 60/40 by weight solution of phenol/tetrachloroethane.
- the anaerobically biodegradable polyesters optionally, may contain the residues of a branching agent.
- the weight percentage ranges for the branching agent are from about 0 to about 2 wt%, about 0.1 to about 1 wt%, or about 0.1 to about 0.5 wt%, based on the total weight of the polyester.
- the branching agent can have a weight average molecular weight of about 50 to about 5000 or about 92 to about 3000, and a functionality of about 3 to about 6.
- the branching agent may be the esterified residue of a polyol having 3 to 6 hydroxyl groups, a polycarboxylic acid having 3 or 4 carboxyl groups (or ester- forming equivalent groups), or a hydroxy acid having a total of 3 to 6 hydroxyl and carboxyl groups.
- Representative low molecular weight polyols that may be employed as branching agents include glycerol, trimethylolpropane, trimethylolethane, polyethertriols, glycerol, 1,2,4-butanetriol, pentaerythritol, 1,2,6-hexanetriol, sorbitol, 1,1,4,4,-tetrakis (hydroxymethyl) cyclohexane, tris(2-hydroxyethyl) isocyanurate, and dipentaerythritol.
- branching agents include glycerol, trimethylolpropane, trimethylolethane, polyethertriols, glycerol, 1,2,4-butanetriol, pentaerythritol, 1,2,6-hexanetriol, sorbitol, 1,1,4,4,-tetrakis (hydroxymethyl) cyclohexane, tris(2-hydroxyethyl) isocyanurate, and dipentaeryth
- Particular branching agent examples of higher molecular weight polyols are triols derived by condensing alkylene oxides having 2 to 3 carbons, such as ethylene oxide and porpylene oxide with polyol initiators.
- Representative polycarboxylic acids that may be used as branching agents include hemimellitic acid, trimellitic (1,2,4-benzenetricarboxylic) acid and anhydride, trimesic (1,3,5-benzenetricarboxylic) acid, pyromellitic acid?
- benzenetetracarboxylic acid benzophenone tetracarboxylic acid, 1,1,2,2-ethanetetracarboxyhc acid, 1,1,2-ethanetricarboxylic acid, 1,3,5- pentanetricarboxylic acid, and 1,2,3,4-cyclopentanetetracarboxylic acid.
- acids may be used as such, they can also be used in the form of their lower alkyl esters or their cyclic anhydrides in those instances where cyclic anhydrides can be formed.
- Branching hydroxycarboxylic acids (these hydroxycarboxylic acids differ from the hydroxycarboxylic acids mentioned elsewhere in this description by not containing an equal number of acid and hydroxy groups, and are excluded from the definition of hydroxycarboxylic acids used elsewhere in this description) that may be used as branching agents include malic acid, citric acid, tartaric acid, 3-hydroxyglutaric acid, mucic acid, trihydroxyglutaric acid, 4-carboxyphthalic anhydride, hydroxyisophthalic acid, and 4-(beta-hydroxyethyl)phthalic acid.
- Such branching hydroxycarboxylic acids contain a combination of 3 or more hydroxyl and carboxyl groups.
- the anaerobically biodegradable polyesters of the invention may also comprise one or more ion-containing monomers to increase their melt viscosity.
- the ion-containing monomer can be selected from salts of sulfoisophthahc acid or a derivative thereof.
- a typical example of this type of monomer is sodiosulfoisophthalic acid or the dimethyl ester of sodiosulfoisophthalic.
- the typical concentration range for ion-containing monomers is about 0.3 to about 5.0 mole% or about 0.3 to about 2.0 mole%, based on the total moles of diacid residues.
- the anaerobically biodegradable polyesters of the instant invention may also comprise from 0 to about 5 wt%, based on the total weight of the polyester, of one or more chain extenders.
- Exemplary chain extenders are divinyl ethers such as those disclosed in U.S. Patent No. 5,817,721 or diisocyanates such as, for example, those disclosed in U.S. Patent No. 6,303,677.
- Representative divinyl ethers are 1,4-butanediol divinyl ether, 1,5- hexanediol divinyl ether, and 1,4-cyclohexandimethanol divinyl ether.
- Representative diisocyanates are toluene 2,4-diisocyanate, toluene 2,6- diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthylene-1,5- diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and methylenebis(2-isocyanatocyclohexane).
- the workable weight percent ranges are about 0.3 to about 3.5 wt%, based on the total weight percent of the polyester, and about 0.5 to about 2.5 wt%. It is also possible in principle to employ trifunctional isocyanate compounds which may contain isocyanurate and/or biurea groups with a functionality of not less than three, or to replace the diisocyanate compounds partially by tri- or polyisocyanates.
- the polyesters of the present invention may be blended with thermoplastic starch to form an anaerobically biodegradable composition.
- the amount of thermoplastic starch in the composition may range from about 5 to about 70 weight percent, based on the weight of the composition. It is expected that blending with thermoplastic starch will increase the rate of biodegradation of the polyester.
- starch has been the subject of increasing interest over recent years. The motivation is keen since starch is an abundant and inexpensive filler material. Moreover, starch may also impart enhanced biodegradability to the resulting blend. These PE and PP polymers, however, are not fit for use in some applications, such as where complete biodegradation is desired.
- Natural starch found in plant products can be isolated as a granular powder. Natural starch can be treated at elevated temperature and pressure with addition of defined amounts of water to form a melt. Such a melt is referred to as gelatinized or destructurized starch. Destructurized starch can be mixed with additives such as plasticizers to obtain a thermoplastic starch or TPS.
- polyesters of the present invention may also be combined with inorganic salts to form an anaerobically biodegradable .
- the composition may comprise at least about 0.1 weight percent of inorganic salts.
- the inorganic salts include metal carbonates, metal oxides, metal phosphates, metal chlorides, metal sulfates, and mixtures thereof.
- Representative metal cations in these inorganic salts may include calcium, potassium, sodium, magnesium, other Group I and II metal cations, aluminum, titanium and silicon.
- Representative inorganic salts include talc, calcium carbonate, magnesium carbonate, potassium carbonate, sodium carbonate, calcium chloride, magnesium chloride, calcium phosphate, titanium oxide, silicone oxide, aluminum oxide, and mixtures thereof.
- the inorganic salt content ranges from about 0.1 to about 60 wt %, from about 1 to about 50 wt %, or from about 2 to about 40 wt %.
- the anaerobically biodegradable composition comprises from about 1 to about 20 wt % calcium carbonate or talc.
- additives include, but are not limited to, processing aids, fillers, surfactants, plasticizers, compatibilizers, impact modifiers, nucleating agents, anti-oxidants, heat or ultraviolet stabilizers, colorants, anti-static agents, lubricants, blowing agents, dispersants, thickening agents, antimicrobials, and mixtures thereof.
- these additives comprise up to about 10 wt %, up to about 20 wt %, or up to about 30 wt %, of the composition of the present invention.
- the polyesters and compositions of this invention can be made into useful articles of manufacture using conventional methods.
- Such articles demonstrate the novel and unexpected ability to disintegrate and subsequently mineralize into carbon dioxide, water, and biomass under partially anaerobic (low oxygen) or completely anaerobic conditions.
- this invention includes not only the uniquely useful polyesters and compositions, but also articles of manufacture made from them.
- Potential articles include, but are not limited to, films, melt-blown webs, spunbond fabrics, bi-component fiber components, adhesive promoting layers, binders for cellulosics, flushable nonwovens and films, dissolvable binder fibers, protective layers, and carriers for active ingredients to be released or dissolved in water. Other extrudable and melt-spun fibrous materials are also possible.
- the processing techniques used for producing the final articles include, but are not limited to, melt-blowing, melt-casting, calendering, and spunbonding. Individual component structures may further be combined to achieve the final article structure using conventional means of joining and construction (e.g., solvent or adhesive bonding with suitable solvents or adhesive systems optionally combined with pressure or heat lamination, coextrusion techniques, or combinations of other conventional bonding/joining techniques used in the industry).
- the polyesters and compositions of the present invention are particularly suitable for use in disposable absorbent articles.
- the term "absorbent articles” refers to articles that absorb and contain body liquids, and more specifically refers to articles that are placed against or in proximity to the body of the wearer to absorb and contain the various liquids discharged from the body.
- the term "disposable absorbent articles” refers to articles that are intended to be discarded after a single use (i.e., the original absorbent article in its whole is not intended to be laundered or otherwise restored or reused as an absorbent article, although certain materials or all of the absorbent article can be recycled, reused, composted or flushed).
- the present invention is applicable to various absorbent articles such as diapers, incontinence briefs, incontinence pads, training pants, pull-on diapers, diaper inserts, catamenial pads, sanitary napkins, pantihners, interlabial devices, tampons, facial tissues, paper towels, breast pads, and the like, as well as other potentially flushable items, such as tampon applicator assemblies (including the barrel and the plunger), tampon cords, wrappers, and packaging for various products, including disposable absorbent articles, disposable gloves, and the like.
- tampon applicator assemblies including the barrel and the plunger
- tampon cords wrappers
- packaging for various products, including disposable absorbent articles, disposable gloves, and the like.
- absorbent articles typically comprise a substantially water- impervious backsheet made from a film of the present invention, a substantially water-permeable topsheet joined to, or otherwise associated with the backsheet, and an absorbent core positioned between the backsheet and the topsheet.
- the topsheet is positioned adjacent to the body-facing surface of the absorbent core.
- the topsheet can be joined to the absorbent core and to the backsheet by attachment means such as those well known in the art.
- th term "joined" encompasses configurations whereby an element is directly secured to the other element by affixing the element directly to the other element, and configurations whereby the element is indirectly secured to the other element by affixing the element to intermediate member(s) which in turn are affixed to the other element.
- the topsheet and the backsheet are joined directly to each other at the periphery thereof.
- the topsheet and backsheet can also be indirectly joined together by directly joining them to the absorbent core by the attachment means.
- Example 1 Microbial Attachment and Fragmentation Analysis Films were prepared from a mixture of adipic acid and terephthalic acid as the diacid components and 100 mole% 1,4-butanediol as the diol component using conventional blown film processing equipment in the Technical Service Laboratory of Eastman Chemical Company.
- the terephthalic acid content and film composition are shown in Table 1.
- the base resin was fed into a 2-1/2" single screw extruder having a 24:1 length: diameter ratio and using a moderate shear, general purpose polyester screw with no mixing and a 3:1 compression : ratio.
- the resin was dried prior to processing in a desiccant dryer at 150°F for 8 hours.
- Process additives were similarly dried prior to processing and delivered to the single screw extrusion process through the use of a gravimetric feeding system.
- the processing additives and their final concentrations in the films are also shown in Table 1.
- the additives were incorporated using appropriate amounts of a concentrate of 50 wt% CaCO 3 in the same resin as the base resin or a concentrate of 50 wt% of talc in the same resin as the base resin.
- the melt was then delivered through a 6-inch monolayer, spiral mandrel die.
- a dual-lip air ring using chilled air and no internal bubble cooling was used to produce film with a 2:1 machine direction/cross direction blow up ratio.
- the film was produced by collapsing the tubular film using a collapsing frame height of 18 feet.
- the films produced from aliphatic- aromatic copolyesters containing 100 mol% 1,4-butanediol, less than 45 mol% terephthalic acid, and greater than 55 mol% adipic acid all demonstrated excellent microbial attachment and film fragmentation.
- Films produced from copolyesters containing 100 mol% 1,4-butanediol, greater than 45 mol% terephthalic acid, and less than 55 mol% adipic acid showed minimal attachment and fragmentation.
- thermoplastic starch Commercially available bags produced from aliphatic-aromatic copolyesters containing 100 mol% 1,4-butanediol, 46-7 mol% terephthalic acid, and 53-4 mol% adipic acid with the addition of high levels (30 wt%) of thermoplastic starch showed no attachment or fragmentation. Complete biodegradation, whether under aerobic or anaerobic (or in between) conditions results in the carbon of the material biodegraded into microbial cell mass and eventually evolved as carbon dioxide.
- Example 2 Radiochemistry Analysis Film Forming Procedure: Three carbon-14 labeled aliphatic-aromatic polyester resins (labeled on aromatic ring carbon) were synthesized using carbon-14 labeled terephthalic acid. The ingredients and method used to make the films are described below.
- REACTOR CHARGE 50ml round bottom 24/40STG
- PROCEDURE 1 Charged flask with items 1, 2, 3, 4, and 5; flushed with N 2 and evacuated with vacuum pump; flush 2X. 2. Heated flask at the following temperatures and times: Temp. °C Time 190 l hr. 200 l hr. 210 1.5 hr. Add ULTRANOX 626 (item 6) Up to 255 30 min. slight vac, vigorous boiling Vac. increased to 0.11 Torr High Temp., High Vac. 1.5 hr.
- the polymer had a light amber color and had increased in viscosity to the point that it was wrapping the stirrer and pulling away from the walls of the flask.
- the top of the polymer mass had the typical swirls or ripples because of the high viscosity.
- the flask was scored with a glass knife around the circumference perpendicular to the neck, cracked with a hot glass bead, and the halves were separated releasing the stirrer with the attached polymer.
- the three resins obtained contain approximately 42 mole% terephthalic acid, 43 mole% terephthalic acid, and 46 mole% terephthalic acid.
- the mole% terephthalic acid was determined using proton NMR (duplicate analyses).
- the resin samples were stored in desiccant under nitrogen, at 0-2°C until dissolved in a 1:3 methanohmethylene chlorine solvent mixture. The samples were solvent cast onto Teflon lined pans and cut into 1x2 inch strips.
- Thickness was controlled by the amount of polyester to solvent poured on to the pans. Six films were cut to keep final thickness to 1.0 mil ⁇ 0.2 mil. Each film represented 0.4 million disintegrations per minute (dpm) ⁇ 1500 dpm (dpm refers to counts of radioactivity per minute adjusted for background collected during that time period).
- the Carbosorb traps were tested weekly for the total dpm counts. Cumulative % of totals were calculated as follows: (current week total counts - previous week's counts) / (total counts in original film). Additional Carbosorb was added to the traps as needed. The material in the traps was kept in the liquid and active microbial state by the addition of 100 cc of septic tank effluent every 30 days. The apparatus and method used were consistent with the D6340 - 98
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Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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JP2007503977A JP2007532699A (en) | 2004-03-19 | 2005-03-10 | Anaerobic biodegradable polyester |
EP05725406A EP1725602A2 (en) | 2004-03-19 | 2005-03-10 | Anaerobically biodegradable polyesters |
Applications Claiming Priority (4)
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US55483804P | 2004-03-19 | 2004-03-19 | |
US60/554,838 | 2004-03-19 | ||
US10/852,502 US20050209374A1 (en) | 2004-03-19 | 2004-05-24 | Anaerobically biodegradable polyesters |
US10/852,502 | 2004-05-24 |
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WO2005092948A2 true WO2005092948A2 (en) | 2005-10-06 |
WO2005092948A3 WO2005092948A3 (en) | 2007-01-04 |
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PCT/US2005/008214 WO2005092948A2 (en) | 2004-03-19 | 2005-03-10 | Anaerobically biodegradable polyesters |
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US (1) | US20050209374A1 (en) |
EP (1) | EP1725602A2 (en) |
JP (1) | JP2007532699A (en) |
WO (1) | WO2005092948A2 (en) |
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Also Published As
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US20050209374A1 (en) | 2005-09-22 |
WO2005092948A3 (en) | 2007-01-04 |
EP1725602A2 (en) | 2006-11-29 |
JP2007532699A (en) | 2007-11-15 |
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