WO2006010063A1 - Sulfonated aromatic copolyesters containing hydroxyalkanoic acid groups and shaped articles produced therefrom - Google Patents

Sulfonated aromatic copolyesters containing hydroxyalkanoic acid groups and shaped articles produced therefrom Download PDF

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Publication number
WO2006010063A1
WO2006010063A1 PCT/US2005/024388 US2005024388W WO2006010063A1 WO 2006010063 A1 WO2006010063 A1 WO 2006010063A1 US 2005024388 W US2005024388 W US 2005024388W WO 2006010063 A1 WO2006010063 A1 WO 2006010063A1
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Prior art keywords
grams
mole percent
reaction mixture
acid
sulfonated aromatic
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PCT/US2005/024388
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English (en)
French (fr)
Inventor
Richard Allen Hayes
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EIDP Inc
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EI Du Pont de Nemours and Co
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Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to CN2005800224957A priority Critical patent/CN1980975B/zh
Priority to DE200560023164 priority patent/DE602005023164D1/de
Priority to AU2005265434A priority patent/AU2005265434B2/en
Priority to JP2007520567A priority patent/JP2008506022A/ja
Priority to EP20050773202 priority patent/EP1769015B1/en
Publication of WO2006010063A1 publication Critical patent/WO2006010063A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C09D167/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • 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
    • 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
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • 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
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1328—Shrinkable or shrunk [e.g., due to heat, solvent, volatile agent, restraint removal, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1372—Randomly noninterengaged or randomly contacting fibers, filaments, particles, or flakes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1376—Foam or porous material containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/31794—Of cross-linked polyester

Definitions

  • the present invention relates to sulfonated aromatic copolyesters that contain hydroxyalkanoic acid groups.
  • the copolyesters can be used to form a variety of shaped articles, which use is also within the scope of the present invention.
  • the glycol component contains about 99.0 to about 1.0 mole percent of a single first glycol component selected from ethylene glycol, 1 ,3-propanediol and 1,4- butanediol and 0 to about 5.0 mole percent of one or more of a second glycol component based on 100 mole percent total glycol component.
  • the filled sulfonated aromatic copolyesters are biodegradable.
  • One preferred aspect of the present invention includes film comprising sulfonated aromatic copolyesters containing between 1.0 to 99.0 mole percent of a hydroxyalkanoic acid component and processes to produce same.
  • the sulfonated aromatic copolyesters can contain fillers.
  • the films of the sulfonated aromatic copolyesters have an optimized balance of physical properties, such as toughness, thermal dimensional stability and moisture barrier, in comparison to films of known sulfonated aromatic copolyesters.
  • the sulfonated aromatic copolyesters consist essentially of 98.9 to 1.0 mole percent of an aromatic dicarboxylic acid component, 1.0 to 99.0 mole percent of a hydroxyalkanoic acid component selected from lactic acid, glycolic acid and mixtures thereof, 99.0 to 1.0 mole percent of a single glycol selected from the group of ethylene glycol, 1 ,3-propanediol, and 1,4-butanediol, 0.1 to 10.0 mole percent of a sulfonate component, 0 to 5.0 mole percent of an other glycol component, 0 to 5.0 mole percent of a polyfunctional branching agent, and optionally an effective amount of a color reducing agent.
  • the sulfonated aromatic copolyesters can contain fillers.
  • the oriented food packaging films of the sulfonated aromatic copolyesters have an optimized balance of physical properties, such as toughness, thermal dimensional stability, deadfold performance, and moisture barrier, in comparison to food packaging films of known sulfonated aromatic copolyesters.
  • a further preferred aspect of the present invention includes the use of films laminated onto substrates comprising sulfonated aromatic copolyesters containing between 1.0 to 99.0 mole percent of a hydroxyalkanoic acid component for food packaging or food service end uses.
  • the substrates may include, for example, paper, paperboard, inorganic foams, organic foams, inorganic-organic foams.
  • the sulfonated aromatic copolyesters consist essentially of 98.9 to 1.0 mole percent of an aromatic dicarboxylic acid component, 1.0 to 99.0 mole percent of a hydroxyalkanoic acid component selected from lactic acid, glycolic acid and mixtures thereof, 99.0 to 1.0 mole percent of a single glycol selected from ethylene glycol, 1,3-propanediol, and 1 ,4-butanediol, 0.1 to 10.0 mole percent of a sulfonate component, 0 to 5.0 mole percent of an other glycol component, 0 to 5.0 mole percent of a polyfunctional branching agent, and optionally an effective amount of a color reducing agent.
  • the aromatic copolyesters consist essentially of 98.9 to 1.0 mole percent of an aromatic dicarboxylic acid component; 1.0 to 99.0 mole percent of a hydroxyalkanoic acid selected from lactic acid, glycolic acid and mixtures thereof; 99 to 1.0 mole percent of a single glycol selected from ethylene glycol, 1 ,3-propanediol, and 1 ,4-butanediol; 0.1 to 10.0 mole percent of a sulfonate component, (based on a total of 100 mole percent of the aromatic dicarboxylic acid component, the hydroxyalkanoic acid component, and the sulfonate component); 0 to 5.0 mole percent of an other glycol component; 0 to 5.0 mole percent of a polyfunctional branching agent; and optionally an effective amount of a color reducing agent component.
  • aromatic dicarboxylic acid and ester there of can be used; however, examples of desirable aromatic dicarboxylic acid components include terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, 2,6-naphthalene dicarboxylic acid, dimethyl-2,6-naphthalate, 2,7-naphthalene dicarboxylic acid, dimethyl-2,7-naphthalate, 3,4'-diphenyl ether dicarboxylic acid, dimethyl-3,4'diphenyl ether dicarboxylate, 4,4'-diphenyl ether dicarboxylic acid, dimethyl-4,4'-diphenyl ether dicarboxylate, 3,4'-diphenyl sulfide dicarboxylic acid, dimethyl-3,4'-diphenyl sulfide dicarboxylate, 4,4'- diphenyl sulfide dicarboxylic acid, dimethyl-4,4'-dipdipheny
  • the sulfonated aromatic copolyester contains between 98.9 and 30 mole percent of the aromatic dicarboxylic acid component. More preferably, the sulfonated aromatic copolyester contains between 98.9 and 50 mole percent of the aromatic dicarboyxlic acid component. Even more preferably, the aromatic copolyester contains between 95 and 50 mole percent of the aromatic dicarboxylic acid component.
  • the optional other glycol component is selected from unsubstituted, substituted, straight chain, branched, cyclic aliphatic, aliphatic-aromatic and aromatic diols having from 2 carbon atoms to 36 carbon atoms.
  • any other glycol known can be used; however, specific examples of desirable other glycol components include ethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,6-hexanediol, 1 ,8-octanediol, 1 ,10- decanediol, 1 ,12-dodecanediol, 1 ,14-tetradecanediol, 1 ,16- hexadecanediol, dimer diol, 4,8-bis(hydroxymethyl)- tricyclo[5.2.1.0/2.6]decane, 1 ,4-cyclohexanedimethanol, isosorbide, di
  • hindered phenolic materials include: 1 ,3,5- trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2-(2 H- benzotriazol-2-yl)-4-(1 , 1 ,3,3-tetramethylbutyl)phenol, 3-tert-butyl-4- hydroxy-5-methylphenyl sulfide, 5-tert-butyl-4-hydroxy-2-methylphenyl sulfide, 2,4-di-tert-butyl-6-(5-chloro-2 H-benzotriazol-2-yl)phenol, 2,2'- ethylidenebis(4,6-di-tert-butylphenol), 4,4'-isopropylidenebis(2,6- dimethylphenol), 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3- tetramethylbut
  • the filler can be added to the polymer of the present invention at any stage during the polymerization of the polymer or after the polymerization is completed.
  • the fillers can be added with the copolyester monomers at the start of the polymerization process. This is preferable for, for example, the silica and titanium dioxide fillers, to provide adequate dispersion of the fillers within the polyester matrix.
  • the filler can be added at an intermediate stage of the polymerization, for example, as the precondensate passes into the polymerization vessel.
  • the filler can be added after the copolyester exits the polymerizer.
  • blendable biodegradable materials include poly(hydroxy alkanoates), polycarbonates, poly(caprolactone), aliphatic polyesters, aliphatic-aromatic copolyesters, aliphatic-aromatic copolyetheresters, aliphatic-aromatic copolyamideesters, sulfonated aliphatic-aromatic copolyesters, sulfonated aliphatic-aromatic copolyetheresters, sulfonated aliphatic-aromatic copolyamideesters, copolymers thereof, and mixtures thereof.
  • a preferred aspect of the present invention relates to film comprising the sulfonated aromatic copolyesters containing hydroxyalkanoic acid residues and production processes thereof and articles derived therefrom.
  • Polymeric films have a variety of uses, such as in packaging, especially of foodstuffs, adhesives tapes, insulators, capacitors, photographic development, x-ray development and as laminates, for example.
  • the heat resistance of the film is an important factor. Therefore, a higher melting point, glass transition temperature, and crystallinity level are desirable to provide better heat resistance and more stable electrical characteristics, along with a rapid biodegradation rate.
  • these films have good barrier properties, for example; moisture barrier, oxygen barrier, and carbon dioxide barrier, good grease resistance, good tensile strength and a high elongation at break.
  • the draw down ratio is defined as the ratio of the die gap to the product of the thickness of the cooled film and the blow-up ratio.
  • Draw down may be induced by tension from pinch rolls.
  • Blow-up ratio is the ratio of the diameter of the cooled film bubble to the diameter of the circular die.
  • the blow up ratio may be as great as 4 to 5, but 2.5 is more typical.
  • the draw down induces molecular orientation within the film in the machine direction, (i.e.; direction of the extrudate flow), and the blow-up ratio induces molecular orientation in the film in the transverse or hoop direction.
  • the quenched bubble moves upward through guiding devices into a set of pinch rolls which flatten it.
  • the resulting sleeve may subsequently be slit along one side, making a larger film width than could be conveniently made via the cast film method.
  • the slit film may be further gusseted and surface-treated in line.
  • the blown film can be produced by more elaborate techniques, such as the double bubble, tape bubble, or trapped bubble processes.
  • the double-bubble process is a technique in which the polymeric tube is first quenched and then reheated and oriented by inflating the polymeric tube above the glass transition temperature, (Tg), but below the crystalline melting temperature, (Tm), of the polyester, (if the polyester is crystalline).
  • Tg glass transition temperature
  • Tm crystalline melting temperature
  • the double bubble technique has been disclosed in the common art, for example, by Pahkle in US 3,456,044.
  • Multilayer films can also be produced, having, for example, bilayer, trilayer, and multilayer film structures.
  • One advantage to multilayer films is that specific properties can be tailored into the film to solve critical use needs. The more costly ingredients can thus be relegated to the outer layers to directly provide the desired properties for the critical needs.
  • the multilayer film structures may be formed through coextrusion, blown film, dipcoating, solution coating, blade, puddle, air-knife, printing, Dahlgren, gravure, powder coating, spraying, or other art processes.
  • the multilayer films are produced by extrusion casting processes. For example, the resin materials are heated in a uniform manner.
  • biodegradable materials suitable as additional layers include poly(hydroxy alkanoates), polycarbonates, poly(caprolactone), aliphatic polyesters, aliphatic-aromatic copolyesters, aliphatic-aromatic copolyetheresters, aliphatic-aromatic copolyamideesters, sulfonated aliphatic-aromatic copolyesters, sulfonated aliphatic-aromatic copolyetheresters, sulfonated aliphatic-aromatic copolyamideesters, copolymers thereof, and mixtures thereof.
  • biodegradable materials suitable as additional layers include the Biomax® sulfonated aliphatic-aromatic copolyesters of the DuPont Company, the Eastar Bio® aliphatic-aromatic copolyesters of the Eastman Chemical Company, the Ecoflex® aliphatic-aromatic copolyesters of the BASF Corporation, poly(1 ,4-butylene terephthalate-co- adipate, (50:50, molar), the EnPol® polyesters of the Ire Chemical Company, poly(1 ,4-butylene succinate), the Bionolle® polyesters of the Showa High Polymer Company, poly(ethylene succinate), poly(1 ,4- butylene adipate-co-succinate), poly(1 ,4-butylene adipate), poly(amide esters), the Bak® poly(amide esters) of the Bayer Company, poly(ethylene carbonate), poly(hydroxybutyrate), poly (hydroxy valerate), poly(hydroxybutylene
  • biaxial orientation can be induced in the film by stretching in both the machine and transverse direction after formation.
  • the machine direction stretch is initiated in forming the film simply by rolling out and taking up the film. This stretches the film in the direction of takeup, orienting some of the fibers. Although this strengthens the film in the machine direction, it allows the film to tear easily in the direction at right angles because all of the fibers are oriented in one direction.
  • the biaxiaily oriented film can further be subjected to additional drawing of the film in the machine direction, in a process known as tensilizing.
  • the biaxial drawing process is conducted continuously at high production rates in multistage roll drawing equipment, as available from Bruckner, wherein the drawing of the extruded film stock takes place in a series of steps between heated rolls rotating at different and increasing rates.
  • the monoaxial stretching is preferably from about 4 to about 20, more preferably from about 4 to about 10.
  • Draw ratio is defined as the ratio of a dimension of a stretched film to a non-stretched film.
  • Uniaxial orientation can be obtained through stretching the film in only one direction in the above-described biaxial processes or by directing the film through a machine direction orienter ("MDO"), commercially available from vendors such as the Marshall and Williams Company of Buffalo, Rhode Island.
  • MDO machine direction orienter
  • the MDO apparatus has a plurality of stretching rollers that progressively stretch and thin the film in the machine direction of the film.
  • Orientation may be enhanced within blown film operations by adjusting the blow-up ratio, (BUR), which is defined as the ratio of the diameter of the film bubble to the die diameter.
  • BUR blow-up ratio
  • Shrinkage can be controlled by holding the film in a stretched position and heating for a few seconds before quenching. This is typically referred to as "heat setting". This heat stabilizes the oriented film, which then may be forced to shrink only at temperatures above the heat stabilization temperature. Further, the film can also be subjected to rolling, calendering, coating, embossing, printing, or any
  • Process conditions and parameters for making films using known methods can be determined by a skilled artisan for any given polymeric composition and desired application.
  • the properties exhibited by a film depend on several factors indicated above, including the polymeric composition, the method of forming the polymer, the method of forming the film, and whether the film was treated for stretch or biaxially oriented.
  • the film can be treated by known, conventional post forming operations, such as corona discharge, chemical treatments, and flame treatment.
  • the films can be used as protective films for agriculture, such as mulch films, seed coverings, agriculture mats containing seeds, ("seed tapes"), garbage and lawn waste bags.
  • protective films include: adhesive tape substrates, bags, bag closures, bed sheets, bottles, cartons, dust bags, fabric softener sheets, garment bags, industrial bags, trash bags, waste bin liners, compost bags, labels, tags, pillow cases, bed liners, bedpan liners, bandages, boxes, handkerchiefs, pouches, wipes, protective clothing, surgical gowns, surgical sheets, surgical sponges, temporary enclosures, temporary siding, toys, and wipes.
  • a particularly preferred use of the films comprising the sulfonated aromatic copolyesters containing hydroxyalkanoic acid residues include food packaging, especially for fast food packaging.
  • food packaging uses include fast food wrappers, stretch wrap films, hermetic seals, food bags, snack bags, grocery bags, cups, trays, cartons, boxes, bottles, crates, food packaging films, blister pack wrappers, skin packaging.
  • a specifically preferred end use for the films is in making wraps.
  • Wraps can be used to enclose meats, other perishable items, and especially fast food items, such as sandwiches, burgers, and dessert items.
  • the films used as wraps combine a balance of physical properties, including: paper-like stiffness combined with sufficient toughness so as not to tear when used to wrap, for example, a sandwich; deadfold characteristics such that once folded, wrapped or otherwise manipulated into the desired shape, the wraps maintain their shape and not tend to spontaneously unfold or unwrap; grease resistance, where desired; and a moisture barrier while not allowing for moisture to condense onto an item wrapped therein.
  • the films can be further processed to produce additional desirable articles, such as containers.
  • the films may be thermoformed as disclosed, for example, in US 3,303,628, US 3,674,626, and US 5,011 ,735.
  • the films may also serve to package foods, such as meats, through vacuum skin packaging techniques, as disclosed in, for example, US 3,835,618, US 3,950,919, US Re 30,009, and US 5,011 ,735.
  • the films can further be laminated onto substrates, as described below.
  • the polymeric coated substrates have a variety of uses, such as in packaging, especially of foodstuffs, and as disposable cups, plates, bowls and cutlery.
  • the heat resistance of the coating is an important factor. Therefore, a higher melting point, glass transition temperature, and crystallinity level are desirable to provide better heat resistance, along with a rapid biodegradation rate. Further, it is desired that the coatings provide good barrier properties for moisture, grease, oxygen, and carbon dioxide, and have good tensile strength and a high elongation at break.
  • Coatings can be made from the sulfonated aromatic copolyesters by any process known.
  • thin coatings may be formed through dipcoating as disclosed in US 4,372,311 and US 4,503,098, extrusion onto substrates, as disclosed, for example, in US 5,294,483, US 5,475,080, US 5,611 ,859, US 5,795,320, US 6,183,814, and US 6,197,380, blade, puddle, air-knife, printing, Dahlgren, gravure, powder coating, spraying, or other art processes.
  • the coatings may be of any thickness.
  • Coatings are preferably formed by solution, dispersion, latex, or emulsion casting; powder coating; or extrusion onto a preformed substrate.
  • a coating of the sulfonated copolyesters can also be applied to substrates by powder coating processes.
  • the sulfonated copolyesters are coated onto the substrates in the form of a powder having a fine particle size.
  • the substrate to be coated can be heated to above the fusion temperature of the polymer and the substrate is dipped into a bed of the powdered polymer fluidized by the passage of air through a porous plate. The fluidized bed is typically not heated.
  • a layer of the polymer adheres to the hot substrate surface and melts to provide the coating.
  • Coating thicknesses can be in the range of about 0.005 inch to 0.080 inch, (0.13 to 2.00 mm).
  • Metal articles of complex shapes can also be coated with the polymeric film by the whirl sintering process.
  • the articles, heated to above the melting point of the polymer are introduced into a fluidized bed of powdered polymer wherein the polymer particles are held in suspension by a rising stream of air, thus depositing a coating on the metal by sintering.
  • Coatings of the sulfonated copolyesters can also be applied by spraying the molten, atomized polymeric composition onto substrates, such as paperboard.
  • substrates such as paperboard.
  • Calendering processes can also be used to produce polymeric laminates onto substrates.
  • Calenders consist of two, three, four, or five hollow rolls arranged for steam heating or water cooling.
  • the polymer to be calendered is softened, for example in a ribbon blender, such as a Banbury mixer.
  • Optional additives can be mixed in, such as plasticizers.
  • the softened polymer is then fed to the rollers and is squeezed into a film.
  • thick sections can be formed by applying one layer of polymer onto a previous layer (double plying).
  • the substrate such as textile or nonwoven fabric or paper, is fed through the last two rolls of the calender so that the resin film is pressed into the substrate.
  • the thickness of the laminate is determined by the gap between the last two rolls of the calender. If desired, the surface can be made glossy, matte, or embossed.
  • the laminate is then cooled and wound up on rolls.
  • the additional layers can contain the sulfonated aromatic copolyesters containing hydroxyalkanoic acid residues or of materials which may be biodegradable or not biodegradable.
  • the materials can be naturally derived, modified naturally derived or synthetic.
  • nonbiodegradable polymeric materials suitable as additional layers are disclosed hereinabove with regard to nobiodedgradable polymeric materials useful in multilayer structures.
  • Polymeric films used as substrates can contain the sulfonated aromatic copolyesters containing hydroxyalkanoic acid residues and/or other materials, which may be biodegradable or not biodegradable.
  • the materials can be naturally derived, modified naturally derived or synthetic.
  • biodegradable, nonbiodegradable and natural materials suitable as substrates include those disclosed hereinabove for use in forming multilayer structures.
  • the substrates can be treated by known, conventional post forming operations, such as corona discharge, chemical treatments, such as primers, flame treatments, adhesives.
  • the substrate layer can be primed with, for example, an aqueous solution of polyethyleneimine, (Adcote® 313), or a styrene-acrylic latex, or flame treated, as disclosed in US 4,957,578 and US 5,868,309.
  • vinyl acetate homopolymer dispersions such as Resyn® 68-5799 and Resyn® 25-2828 by ICI
  • polyvinyl chloride emulsions such as Vycar® 460x24, Vycar® 460x6 and Vycar® 460x58 by the B. F. Goodrich Company
  • polyvinylidene fluoride dispersions such as Kynar® 32 by EIf Atochem
  • ethylene acrylic acid dispersions such as Adcote® 50T4990 and
  • Water-resistant polymer coated paper and paperboard are commonly used in packaging material for foodstuffs and as disposable containers. Coating polymers and multilamellar coating structures including such coated paper and paperboard provide oxygen, water vapor, and aroma tightness for preservation of the packaged product.
  • Coatings made from the sulfonated aromatic copolyesters containing hydroxyalkanoic acid residues can be used in a wide variety of areas such as those disclosed hereinabove for uses of films.
  • wraps may take the form of a polymeric coated paper.
  • Uses and characteristics of coated wraps include those recited hereinabove with respect to films.
  • the wraps can be filled, with, for example, inorganic particles, organic particles, such as starch, or combinations of fillers.
  • the substrate can be shaped into the shape for their intended use, such as in the form of a plate, cup, bowl, or tray, or can be in an intermediate shape still to be formed, such as a sheet or film, when the preformed film is applied.
  • the film can be attached to the substrate using the application of heat and/or pressure, as with, for example heated bonding rolls.
  • the laminate bond strength or peel strength can be enhanced through the use of higher temperatures and/or pressures.
  • the adhesives can be hot melt adhesives or solvent based adhesives.
  • the films and/or the substrates can be treated by known, conventional post forming operations, such as corona discharge, chemical treatments, such as primers, flame treatments, as previously described.
  • US 4,147,836 discloses subjecting a paperboard to a corona discharge to enhance the lamination process with a poly(ethylene terephthalate) film.
  • Quick, et al., in US 4,900,594, disclose the corona treatment of a polyester film to aid in the lamination to paperstock with adhesives.
  • Schirmer, in US 5,011,735, discloses the use of corona treatments to aid the adhesion between various blown films.
  • US 5,679,201 and US 6,071 ,577 disclose the use of flame treatments to aid in the adhesion within polymeric lamination processes.
  • Sandstrom, et al., in US 5,868,309 disclose the use of paperboard substrate primer consisting of certain styrene-acrylic materials to improve the adhesion with polymeric laminates.
  • the films can be passed through heating and pressure/nip rolls to be laminated onto flat substrates. More commonly, the films are laminated onto substrates by processes that are derivatives of thermoforming.
  • the films can be laminated onto substrates by vacuum lamination, pressure lamination, blow lamination, or mechanical lamination. When the films are heated, they soften and can be stretched onto a substrate of any given shape. Processes to adhere a polymeric film to a preformed substrate are disclosed, for example, in US 2,590,221.
  • a plug assist can be used for substrate shapes that require a deep draw, such as cups, deep bowls, boxes, cartons.
  • the softened film tends to thin out significantly before it reaches the base or bottom of the substrate shape, leaving only a thin and weak laminate on the bottom of the substrate shape.
  • a plug assist is any type of mechanical helper that carries more film stock toward an area of the substrate shape where the lamination would otherwise be too thin. Plug assist methods can be adapted to vacuum and pressure lamination processes.
  • the film In pressure lamination, the film can be clamped, heated until it softens, and then forced into the contours of the substrate to be laminated by the application of pressure to the side of the film opposite to the substrate. Exhaust holes may be present to allow the trapped air to escape, or in the more common situation, the substrate is porous to air and the air simply escapes through the substrate. The air pressure may be released once the laminated substrate cools and the film solidifies. Pressure lamination can provide a faster production cycle, improved part definition and greater dimensional control in comparison to vacuum lamination. Pressure lamination of films onto preformed substrates is disclosed, for example, in US 3,657,044 and US 4,862,671.
  • Mechanical lamination includes any lamination method that does not use vacuum or air pressure.
  • the film is heated and then mechanically applied to the substrate. Examples of the mechanical application include molds or pressure rolls.
  • Suitable substrates include articles made of paper, paperboard, cardboard, fiberboard, cellulose, such as Cellophane® cellophane, starch, plastic, polystyrene foam, glass, metal in, for example aluminum or tin cans or metal foils, polymeric foams, organic foams, inorganic foams, organic-inorganic foams, and polymeric films.
  • biodegradable substrates such as paper, paperboard, cardboard, cellulose, and starch
  • biobenign substrates such as inorganic and inorganic-organic foams.
  • Polymeric films suitable as substrates for lamination can be naturally derived, modified naturally derived or synthetic, as disclosed hereinabove.
  • the laminated substrates can be formed into the desired shape using known processes, such as press forming or folding up. Such processes are disclosed, for example in US 3,924,013, US 4,026,458, and US 4,456,164. Quick, et al., in US 4,900,594, disclose the production of trays from flat, polyester laminated paperstock through the use of pressure and heat.
  • the film can be coated with an adhesive using conventional coating technologies or coextrusion, and/ or the substrate can be coated with an adhesive.
  • the sulfonated aromatic copolyesters can also be formed into sheets.
  • Polymeric sheets have a variety of uses, such as in signage, glazings, thermoforming articles, displays and display substrates. For some uses, heat resistance of the sheet is desired. Therefore, a higher melting point, glass transition temperature, and crystallinity level are desirable to provide better heat resistance and greater stability. Further, some uses require that the sheets have ultraviolet (UV) and scratch resistance, g tensile strength, optical clarity, and impact strength, particularly at low temperatures.
  • UV ultraviolet
  • scratch resistance g tensile strength, optical clarity, and impact strength
  • the sheets can be thermoformed by any known method into any desirable shape, for use as, for example, covers, skylights, shaped greenhouse glazings, displays, and food trays.
  • the thermoforming is accomplished by heating the sheet to a sufficient temperature and for sufficient time to soften the copolyester so that the sheet can be easily molded into the desired shape.
  • One of ordinary skill in the art can 'determine appropriate " thermoforming parameters depending upon the viscosity and crystallization characteristics of the polyester sheet.
  • reaction mixture was stirred at 180 C for 1.0 hour under a slow nitrogen purge.
  • the reaction mixture was then heated to 240 C over 0.3 hours with stirring.
  • the reaction mixture was stirred at 240 C for 0.7 hours under a slow nitrogen purge. 12.4 grams of a colorless distillate was collected over this heating cycle.
  • the reaction mixture was then staged to full vacuum with stirring at 240 C.
  • the resulting reaction mixture was stirred for 4.2 hours under full vacuum, (pressure less than 100 mtorr). The vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature. An additional 68.3 grams of distillate was recovered and 92.4 grams of a solid product was recovered.
  • the sample was measured for laboratory relative viscosity, (LRV), as described above and was found to have an LRV of 18.54. This sample was calculated to have an inherent viscosity of 0.58 dL/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis.
  • a glass transition temperature, (Tg) was observed with an onset of 30.4 C, a midpoint of 33.4 C, and an endpoint of 36.3 C.
  • a crystalline melting temperature, ( Tm) was observed at 192.0 C, (17.5 J/g).
  • Example 10 demonstrates the thermal properties of the sulfonated aromatic copolyesters Example 10, which represents the present invention, was found to have a 40 degree C improvement in the glass transition temperature and a 29 degree C improvement in the crystalline melting point temperature over that of materials such as that prepared according to Comparative Example CE 5.
  • the sample was ground into powder and tested for biodegradation, as described above. This sample was found to biodegrade 6.2 percent within 13.6 days under these test conditions.
  • Pressed films were produced from the material prepared above on a Sargent hydraulic melt press, (W. H. Sargent & Company, Chicago, USA). Approximately 0.5 grams of the material prepared above was placed between two sheets of Armalon® cloth with a 0.001 inch thick brass shim. This construct was placed between the hydraulic melt press platens heated to a temperature of 250 C +/- 5 C. The platens were closed without pressure for 10-15 seconds and then the pressure was slowly raised to 3000-4000 psi. The pressure was held there for 15 seconds and then the pressure was released, the sample removed from the hydraulic press and the film was quenched in cold water. The films were found to be clear and flexible.
  • reaction mixture was stirred at 180 C for 1.2 hours under a slow nitrogen purge.
  • the reaction mixture was then heated to 240 C over 0.2 hours with stirring.
  • the reaction mixture was stirred at 240 C for 0.8 hours under a slow nitrogen purge.
  • the reaction mixture was then heated to 255 C over 0.2 hours with stirring under a slight nitrogen purge.
  • the reaction mixture was stirred at 255 C for 0.7 hours under a slight nitrogen purge. 29.3 grams of a colorless distillate was collected over this heating cycle.
  • the reaction mixture was then staged to full vacuum with stirring at 255 C.
  • the resulting reaction mixture was stirred for 3.1 hours under full vacuum, (pressure less than 100 mtorr).
  • the vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature. An additional 51.8 grams of distillate was recovered and 103.8 grams of a solid product was recovered.
  • the sample was measured for laboratory relative viscosity, (LRV), as described above and was found to have an LRV of 13.03. This sample was calculated to have an inherent viscosity of 0.48 dl_/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis.
  • a glass transition temperature, (Tg) was observed with an onset of 68.6 C, a midpoint of 71.0 C, and an endpoint of 73.1 C.
  • a crystalline melting temperature, ( Tm) was observed at 224.5 C, (31.6
  • This sample was calculated to have an inherent viscosity of 0.28 dl_/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis.
  • a glass transition temperature, (Tg) was observed with an onset of 68.8 C, a midpoint of 72.0 C, and an endpoint of 75.3 C.
  • a crystalline melting temperature, ( Tm) was observed at 219.0 C, (9.4 J/g).
  • the resulting reaction mixture was stirred for 1.7 hours under full vacuum, (pressure less than 100 mtorr). The vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature. An additional 54.6 grams of distillate was recovered and 97.4 grams of a solid product was recovered.
  • the sample was measured for laboratory relative viscosity, (LRV), as described above and was found to have an LRV of 14.00. This sample was calculated to have an inherent viscosity of 0.50 dL/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis. A glass transition temperature, (Tg), was observed with an onset of 77.4 C, a midpoint of 78.6 C, and an endpoint of 79.8 C. A crystalline melting temperature, ( Tm), was observed at 225.5 C, (15.5 J/g).
  • the vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature. An additional 53.8 grams of distillate was recovered and 112.6 grams of a solid product was recovered.
  • the sample was measured for laboratory relative viscosity, (LRV), as described above and was found to have an LRV of 14.28. This sample was calculated to have an inherent viscosity of 0.50 dl_/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis.
  • a glass transition temperature, (Tg) was observed with an onset of 70.6 C, a midpoint of 72.8 C, and an endpoint of 75.1 C.
  • a crystalline melting temperature, ( Tm) was observed at 207.3 C, (17.5
  • reaction mixture was stirred at 200 C for 0.9 hours under a slow nitrogen purge.
  • the reaction mixture was then heated to 275 C over 0.5 hours with stirring under a slight nitrogen purge.
  • the reaction mixture was stirred at 275 C for 1.3 hours under a slight nitrogen purge. 24.4 grams of a colorless distillate was collected over this heating cycle.
  • the reaction mixture was then staged to full vacuum with stirring at 275 C.
  • the resulting reaction mixture was stirred for 1.6 hours under full vacuum, (pressure less than 100 mtorr). The vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature. An additional 36.1 grams of distillate was recovered and 129.1 grams of a solid product was recovered.
  • the reaction mixture was then heated to 255 C over 1.1 hours with stirring. After achieving 255 C, the reaction mixture was stirred at 255 C for 0.5 hours under a slow nitrogen purge. 41.3 grams of a colorless distillate was collected over this heating cycle. The reaction mixture was then staged to full vacuum with stirring at 255 C. The resulting reaction mixture was stirred for 3.0 hours under full vacuum, (pressure less than 100 mtorr). The vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature. An additional 55.2 grams of distillate was recovered and 91.2 grams of a solid, tan product was recovered. The sample was measured for laboratory relative viscosity, (LRV), as described above and was found to have an LRV of 13.69.
  • LRV laboratory relative viscosity
  • This sample was calculated to have an inherent viscosity of 0.49 dl_/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis.
  • a glass transition temperature, (Tg) was observed with an onset of 72.8 C, a midpoint of 75.0 C, and an endpoint of 77.2 C.
  • a crystalline melting temperature, ( Tm) was observed at a temperature of 215.2 C, (13.6 J/g).
  • reaction mixture was stirred at 180 C for 1.1 hours under a slight nitrogen purge.
  • the reaction mixture was then heated to 225 C over 0.7 hours with stirring, After achieving 225 C, the reaction mixture was stirred at 225 C for 0.5 hours under a slight nitrogen purge.
  • the reaction mixture was then heated to 255 C over 0.5 hours with stirring. After achieving 255 C, the reaction mixture was stirred at 255 C for 0.6 hours under a slow nitrogen purge. 41.5 grams of a colorless distillate was collected over this heating cycle.
  • the reaction mixture was then staged to full vacuum with stirring at 255 C.
  • the resulting reaction mixture was stirred for 2.5 hours under full vacuum, (pressure less than 100 mtorr).
  • reaction mixture was stirred at 180 C for 0.3 hours under a slight nitrogen purge.
  • the reaction mixture was then heated to 225 C over 0.3 hours with stirring, After achieving 225 C, the reaction mixture was stirred at 225 C for 0.7 hours under a slight nitrogen purge.
  • the reaction mixture was then heated to 255 C over 0.3 hours with stirring. After achieving 255 C, the reaction mixture was stirred at 255 C for 0.9 hours under a slow nitrogen purge. 24.8 grams of a colorless distillate was collected over this heating cycle.
  • the reaction mixture was then staged to full vacuum with stirring at 255 C.
  • the resulting reaction mixture was stirred for 2.8 hours under full vacuum, (pressure less than 100 mtorr).
  • the vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature.
  • the sample was measured for laboratory relative viscosity, (LRV), as described above and was found to have an LRV of 14.51. This sample was calculated to have an inherent viscosity of 0.51 dl_/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis.
  • a glass transition temperature, (Tg) was observed with an onset of 72.2 C, a midpoint of 75.0 C, and an endpoint of 77.8 C.
  • a crystalline melting temperature, ( Tm) was observed at a temperature of 214.2 C, (7.5 J/g).
  • the reaction mixture was stirred and heated to 180 C under a slow nitrogen purge. After achieving 180 C, the reaction mixture was stirred at 180 C for 0.1 hours under a slight nitrogen purge. The reaction mixture was then heated to 225 C over 0.2 hours with stirring, After achieving 225 C, the reaction mixture was stirred at 225 C for 1.1 hours under a slight nitrogen purge. The reaction mixture was then heated to 255 C over 0.5 hours with stirring. After achieving 255 C, the reaction mixture was stirred at 255 C for 0.8 hours under a slow nitrogen purge. 34.9 grams of a colorless distillate was collected over this heating cycle. The reaction mixture was then staged to full vacuum with stirring at 255 C.
  • the resulting reaction mixture was stirred for 2.7 hours under full vacuum, (pressure less than 100 mtorr). The vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature. An additional 56.1 grams of distillate was recovered and 88.4 grams of a solid, light tan product was recovered.
  • the sample was measured for laboratory relative viscosity, (LRV), as described above and was found to have an LRV of 15.01. This sample was calculated to have an inherent viscosity of 0.52 dL/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis. A glass transition temperature, (Tg), was observed with an onset of 70.8 C, a midpoint of 73.7 C, and an endpoint of 76.6 C. A crystalline melting temperature, ( Tm), was observed at a temperature of 210.8 C, (6.4 J/g).
  • the resulting reaction mixture was stirred for 2.7 hours under full vacuum, (pressure less than 100 mtorr). The vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature. An additional 52.8 grams of distillate was recovered and 91.2 grams of a solid, light tan product was recovered.
  • the sample was measured for laboratory relative viscosity, (LRV), as described above and was found to have an LRV of 14.36. This sample was calculated to have an inherent viscosity of 0.51 dL/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis. A glass transition temperature, (Tg), was observed with an onset of 73.0 C, a midpoint of 74.8 C, and an endpoint of 76.5 C. A crystalline melting temperature, ( Tm), was observed at a temperature of 210.8 C, (15.2 J/g).
  • reaction mixture was then heated to 225 C over 0.8 hours with stirring, After achieving 225 C, the reaction mixture was stirred at 225 C for 0.6 hours under a slight nitrogen purge. The reaction mixture was then heated to 255 C over 0.7 hours with stirring. After achieving 255 C, the reaction mixture was stirred at 255 C for 0.5 hours under a slow nitrogen purge. 39.0 grams of a colorless distillate was collected over this heating cycle. The reaction mixture was then staged to full vacuum with stirring at 255 C. The resulting reaction mixture was stirred for 2.6 hours under full vacuum, (pressure less than 100 mtorr). The vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature.
  • the reaction mixture was then heated to 275 C over 0.8 hours with stirring under a slight nitrogen purge.
  • the reaction mixture was stirred at 275 C for 1.1 hours under a slight nitrogen purge. 22.6 grams of a colorless distillate was collected over this heating cycle.
  • the reaction mixture was then staged to full vacuum with stirring at 275 C.
  • the resulting reaction mixture was stirred for 1.9 hours under full vacuum, (pressure less than 100 mtorr).
  • the vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature.
  • An additional 24.9 grams of distillate was recovered and 133.9 grams of a solid product was recovered.
  • the sample was measured for laboratory relative viscosity, (LRV), as described above and was found to have an LRV of 11.88.
  • LRV laboratory relative viscosity
  • This sample was calculated to have an inherent viscosity of 0.50 dL/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis.
  • a glass transition temperature, (Tg) was observed with an onset of 61.5, a midpoint of 64.4 C, and an endpoint of 67.3 C.
  • This sample was calculated to have an inherent viscosity of 0.56 dL/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis.
  • a glass transition temperature, (Tg) was observed with an onset of 68.9 C, a midpoint of 74.2 C, and an endpoint of 79.5 C.
  • a crystalline melting temperature, ( Tm) was observed at a temperature of 243.7 C, (26.8 J/g).
  • the reaction mixture was then heated to 190 C over 0.2 hours with stirring. After achieving 190 C, the reaction mixture was stirred at 190 C for 0.4 hours under a slow nitrogen purge. The reaction mixture was then heated to 200 C over 0.1 hours with stirring under a slight nitrogen purge. After achieving 200 C, the reaction mixture was stirred at 200 C for 0.4 hours under a slight nitrogen purge. The reaction mixture was then heated to 255 C over 0.4 hours with stirring under a slight nitrogen purge. The reaction mixture was stirred at 255 C for 0.8 hours under a slight nitrogen purge. 34.0 grams of a colorless distillate was collected over this heating cycle. The reaction mixture was then staged to full vacuum with stirring at 255 C.
  • the resulting reaction mixture was stirred for 2.0 hours under full vacuum, (pressure less than 100 mtorr). The vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature. An additional 10.1 grams of distillate was recovered and 94.2 grams of a solid product was recovered.
  • the sample was measured for laboratory relative viscosity, (LRV), as described above and was found to have an LRV of 21.97. This sample was calculated to have an inherent viscosity of 0.64 dl_/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis. A glass transition temperature, (Tg), was observed with an onset of 44.7 C, a midpoint of 46.7 C, and an endpoint of 48.8 C. A broad crystalline melting temperature, ( Tm), was observed at 216.7 C, (38.3 J/g).
  • the reaction mixture was then heated to 190 C over 0.2 hours with stirring. After achieving 190 C, the reaction mixture was stirred at 190 C for 0.5 hours under a slow nitrogen purge. The reaction mixture was then heated to 200 C over 0.3 hours with stirring under a slight nitrogen purge. After achieving 200 C, the reaction mixture was stirred at 200 C for 0.6 hours under a slight nitrogen purge. The reaction mixture was then heated to 255 C over 1.0 hour with stirring under a slight nitrogen purge. The reaction mixture was stirred at 255 C for 0.5 hours under a slight nitrogen purge. 33.7 grams of a colorless distillate was collected over this heating cycle. The reaction mixture was then staged to full vacuum with stirring at 255 C.
  • the resulting reaction mixture was stirred for 1.8 hours under full vacuum, (pressure less than 100 mtorr). The vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature. An additional 19.4 grams of distillate was recovered and 91.0 grams of a solid product was recovered.
  • the sample was measured for laboratory relative viscosity, (LRV), as described above and was found to have an LRV of 19.45. This sample was calculated to have an inherent viscosity of 0.60 dL/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis. A glass transition temperature, (Tg), was observed with an onset of 45.0 C, a midpoint of 46.9 C, and an endpoint of 48.9 C. A broad crystalline melting temperature, ( Tm), was observed at 216.3 C, (42.4 J/g).
  • the resulting reaction mixture was stirred for 4.2 hours under full vacuum, (pressure less than 100 mtorr). The vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature. 3.4 grams of additional distillates were recovered and 148.0 grams of a solid product was recovered.
  • the sample was measured for laboratory relative viscosity, (LRV), as described above and was found to have an LRV of 20.59. This sample was calculated to have an inherent viscosity of 0.62 dL/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis. A glass transition temperature, (Tg), was observed with an onset at 37.4 C, a midpoint at 39.2 C, and an endpoint of 40.9 C. A crystalline melting temperature, ( Tm), was observed at 185.9 C, (31.9 J/g).
  • dimethyl terephthalate (90.88 grams), lactic acid, (85 weight percent aqueous solution, 6.36 grams), glycolic acid, (4.56 grams), dimethyl 5-sulfoisophthalate, sodium salt, (3.55 grams), 1 ,4-butanediol, (86.52 grams), and titanium(IV) isopropoxide, (0.1361 grams).
  • the reaction mixture was stirred and heated to 180 C under a slow nitrogen purge. After achieving 180 C, the reaction mixture was stirred at 180 C for 0.6 hours under a slow nitrogen purge. The reaction mixture was then heated to 190 C over 0.3 hours with stirring.
  • the resulting reaction mixture was stirred for 2.8 hours under full vacuum, (pressure less than 100 mtorr). The vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature. 0.3 grams of additional distillates were recovered and 145.1 grams of a solid product was recovered.
  • the sample was measured for laboratory relative viscosity, (LRV), as described above and was found to have an LRV of 11.74. This sample was calculated to have an inherent viscosity of 0.46 dL/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis. A crystalline melting temperature, ( Tm), was observed at 204.0 C, (32.0 J/g).
  • This sample was calculated to have an inherent viscosity of 0.51 dL/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis.
  • a glass transition temperature, (Tg) was observed with an onset of 78.5 C, a midpoint of 78.9 C, and an endpoint of 79.0 C.
  • a crystalline melting temperature, ( Tm) was observed at 241.5 C, (32.7 J/g).
  • This sample was calculated to have an inherent viscosity of 0.56 dL/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis.
  • a broad crystalline melting point, (Tm) was observed at 241.3 C, (28.7 J/g).
  • the reaction mixture was stirred at 275 C for 0.9 hours under a slight nitrogen purge. 24.4 grams of a colorless distillate was collected over this heating cycle. The reaction mixture was then staged to full vacuum with stirring at 275 C. The resulting reaction mixture was stirred for 1.8 hours under full vacuum, (pressure less than 100 mtorr). The vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature. An additional 28.6 grams of distillate was recovered and 116.5 grams of a solid product was recovered. The sample was measured for laboratory relative viscosity, (LRV), as described above and was found to have an LRV of 17.63. This sample was calculated to have an inherent viscosity of 0.56 dL/g.
  • LRV laboratory relative viscosity
  • the sample was ground into powder and tested for biodegradation, as described above. This sample was found to biodegrade 16.0 percent within 27.3 days under these test conditions.
  • reaction mixture was stirred at 200 C for 1.0 hour under a slow nitrogen purge.
  • the reaction mixture was then heated to 275 C over 0.5 hours with stirring under a slight nitrogen purge.
  • the reaction mixture was stirred at 275 C for 1.0 hour under a slight nitrogen purge. 25.6 grams of a colorless distillate was collected over this heating cycle.
  • the reaction mixture was then staged to full vacuum with stirring at 275 C.
  • the resulting reaction mixture was stirred for 0.8 hours under full vacuum, (pressure less than 100 mtorr). The vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature. An additional 20.0 grams of ⁇ istmaie was recovere ⁇ and 14 ⁇ 8 grams of a solid product was recovered.
  • the sample was measured for laboratory relative viscosity, (LRV), as described above and was found to have an LRV of 21.64. This sample was calculated to have an inherent viscosity of 0.64 dL/g.
  • the sample underwent differential scanning calorimetry, (DSC), analysis.
  • a glass transition temperature, (Tg) was observed with an onset of 67.1 C, a midpoint of 70.4 C, and an endpoint of 73.7 C.
  • a crystalline melting temperature, ( Tm) was observed at 211.9 C, (14.3 J/g).
  • the sample was ground into powder and tested for biodegradation, as described above. This sample was found to biodegrade 27.3 percent within 27.3 days under these test conditions.
  • Example 37 demonstrates the enhanced biodegradation rates of polymers made according to the present invention over comparable non- sulfonated materials of the art.
  • Example 37 was found to have an enhanced biodegradation rate in comparison to conventional non- sulfonated polyesters such as that prepared according to Comparative Example CE 7.
  • the reaction mixture was then heated to 275 C over 0.9 hours with stirring under a slight nitrogen purge.
  • the reaction mixture was stirred at 275 C for 0.9 hours under a slight nitrogen purge. 28.1 grams of a colorless distillate was collected over this heating cycle.
  • the reaction mixture was then staged to full vacuum with stirring at 275 C.
  • the resulting reaction mixture was stirred for 1.4 hours under full vacuum, (pressure less than 100 mtorr).
  • the vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature.
  • An additional 33.1 grams of distillate was recovered and 149.9 grams of a solid product was recovered.
  • the sample was measured for laboratory relative viscosity, (LRV), as described above and was found to have an LRV of 15.09.
  • LRV laboratory relative viscosity
  • This sample was calculated to have an inherent viscosity of 0.52 dL/g.
  • the sample underwent differential scanning calorimetry, (DSC) 1 analysis.
  • a glass transition temperature, (Tg) was observed with an onset of 65.6 C, a midpoint of 68.3 C, and an endpoint of 71.0 C.
  • a crystalline melting temperature, ( Tm) was not observed up to a temperature of 300 C.
  • reaction mixture was stirred at 200 C for 1.0 hour under a slow nitrogen purge.
  • the reaction mixture was then heated to 275 C over 1.0 hour with stirring under a slight nitrogen purge.
  • the reaction mixture was stirred at 275 C for 1.0 hour under a slight nitrogen purge. 26.6 grams of a colorless distillate was collected over this heating cycle.
  • the reaction mixture was then staged to full vacuum with stirring at 275 C.
  • the resulting reaction mixture was stirred for 0.6 hours under full vacuum, (pressure less than 100 mtorr). The vacuum was then released with nitrogen and the reaction mass allowed to cool to room temperature. An additional 22.6 grams of distillate was recovered and 86.6 grams of a solid product was recovered.
  • the sample was measured for laboratory relative viscosity, (LRV), as described above and was found to be too viscous to evidence a determination.
  • the sample underwent differential scanning calorimetry, (DSC), analysis.
  • a glass transition temperature, (Tg) was observed with an onset of 66.9 C, a midpoint of 69.5 C, and an endpoint of 72.3 C.
  • a crystalline melting temperature, ( Tm) was not observed up to a temperature of 300 C.
  • Example 40 Example 40.
  • the sample was ground into powder and tested for biodegradation, as described above, and degraded 61.0 percent within 27.3 days.
  • reaction mixture (110.11 grams), glycolic acid, (2.28 grams), dimethyl 5-sulfoisophthalate, sodium salt, (0.89 grams), 1,3-propanediol, (73.06 grams), and titanium(IV) isopropoxide, (0.1500 grams).
  • the reaction mixture was stirred and heated to 180 C under a slow nitrogen purge. After achieving 180 C, the reaction mixture was stirred at 180 C for 0.3 hours under a slow nitrogen purge. The reaction mixture was then heated to 190 C over 0.1 hours with stirring. After achieving 190 C, the reaction mixture was stirred at 190 C for 0.4 hours under a slow nitrogen purge. The reaction mixture was then heated to 200 C over 0.1 hours with stirring under a slight nitrogen purge.
  • reaction mixture was stirred at 200 C for 0.2 hours under a slight nitrogen purge.
  • the reaction mixture was then heated to 255 C over 0.4 hours with stirring under a slight nitrogen purge.
  • the reaction mixture was stirred at 255 C for 0.9 hours under a slight nitrogen purge.
  • Claytone® 2000 (31.86 grams), was then added and the resulting reaction mixture allowed to stir at 255 C for an additional 0.8 hours under a slight nitrogen purge. 35.3 grams of a colorless distillate was collected over this heating cycle.
  • the reaction mixture was then staged to full vacuum with stirring at 255 C.
  • the resulting reaction mixture was stirred for 0.8 hours under full vacuum, (pressure less than 100 mtorr).
  • reaction mixture was stirred at 190 C for 0.4 hours under a slow nitrogen purge.
  • the reaction mixture was then heated to 200 C over 0.1 hours with stirring under a slight nitrogen purge.
  • the reaction mixture was stirred at 200 C for 1.0 hour under a slight nitrogen purge.
  • the reaction mixture was then heated to 255 C over 0.7 hours with stirring under a slight nitrogen purge.
  • the reaction mixture was stirred at 255 C for 0.8 hours under a slight nitrogen purge.
  • Cloisite Na 1 31.86 grams was then added to the stirred reaction mixture at 255 C.
  • the resulting reaction mixture was stirred at 255 C under a slight nitrogen purge for an additional 0.7 hours.
  • Material produced as described for Example 19, above, except at a larger scale, is dried in a hopper dryer for 8 hours at 70 0 C to a - 40 0 C dew point.
  • the material is then fed at a rate of 20 pounds per hour into the feed section of a 1 Va -inch diameter single screw Davis Standard extruder, (screw L/D of 24:1 , model number DS-15H).
  • the extruder conditions and temperature profile is noted below.
  • the molten polymer is then fed into a Killion 3 roll stack sheet line with the conditions and temperature profile noted below.
  • the film is tested as a fast food sandwich wrap packaging .
  • Polymers prepared as described above in the Examples and Comparative Examples noted below in Table 1 are dried in a hopper dryer for 8 hours at 60 C to a - 40 C dew point.
  • the materials are placed in the hopper of a single screw volumetric feeder, (K- tron Model No. 7), from which they free fall to the inlet of a 28 mm Werner and Pfleider twin screw extruder with a vacuum port maintained at house vacuum attached to a 10 inch wide film die with about a 0.010 inch gap.
  • a dry nitrogen purge is maintained in the feed hopper and the feed throat of the extruder.
  • the extruder is operated at a 150 rpm screw speed with the heater profile noted within Table 1. Table !
  • Pieces of the films of Examples 45 to 67 (8-inch by 8-inch squares) are placed in a rotary composter with about 0.5 cubic yards squared of mixed municipal solid waste, (from which glass, cans, and much of the light plastic and paper is removed), and sewage sludge in the ratio of about 2:1.
  • the composter is rotated once a week and the temperature and moisture content is monitored.
  • the material is placed in the hopper of a single screw volumetric feeder, (K-tron Model No. 7), from which it free falls to the inlet of a 28 mm Werner and Pfleider twin screw extruder with a vacuum port maintained at house vacuum attached to a 10 inch wide film die with about a 0.010 inch gap.
  • a dry nitrogen purge is maintained in the feed hopper and the feed throat of the extruder.
  • the extruder is operated at a 150 rpm screw speed with a heater profile as follows:
  • the films produced in the Examples listed below in Table 2, with a thickness of about 1.5 mils to 8 mils, are sent through a Machine Direction Orienter (MDO) Model Number 7200 from the Marshall and Williams Company of Buffalo, Rhode Island.
  • MDO Machine Direction Orienter
  • the MDO unit is preheated to the temperature listed in Table 2, below, and the film is stretched as noted below in Table 2 while at that temperature.
  • “Stretched 3X” means that a 1 meter long film would be stretched to a length of 3 meters.
  • the uniaxially stretched films of Examples 69 to 89 are tested as a fast food sandwich wrap packaging. 10 inch by 16 inch rectangles are cut out of the film of Examples 69 - 89 and Comparative Examples CE 10 - CE 11 and the size accurately measured. The film rectangles are placed in a Fisher Scientific lsotemp Incubator, Model Number 625D, heated to 60 C for 1 hour. The film rectangles are then accurately remeasured. Examples 90 - 97.
  • Zone 1 Zone 2 Zone 3 Zone 4 Zone 5 Die (C) (C) (C) (C) (C) (C) (C) (C) (C) (C)
  • Corn starch (Corn Products 3005 from CPC International, Inc.) and rice starch (Sigma Chemicals catalog number S7260) are dried in a large tray vacuum oven at 90 0 C and less than 1 mm Hg vacuum to a moisture content of less than 1 percent and stored in sealed containers until used.
  • Example 125 is composed of a tumbled blend of 50 weight percent of Example 35 and 50 weight percent of
  • Example 118 A dry nitrogen purge is maintained in the feed hopper and the feed throat of the extruder.
  • the extruder is operated at a 150 rpm screw speed with a heater profile of
  • the extruded polymer films are electrostatically pinned on an 12 inch diameter smooth quench drum maintained at a temperature of 26 C with cold water and collected on release paper using a standard tension roll.
  • the quench drum speed is adjusted from 5 to 15 feet per minute to obtain film samples with a thickness of about 8 mils to about 1.5 mils.
  • the films are tested as fast food sandwich packaging.
  • the dried polymers are fed to a laboratory scale blown film line consisting of a Killion 1.25 inch diameter extruder with a 15:1 gear reducer.
  • the extruder heater zones are set around the temperature noted below in Table 11.
  • the screw is a Maddock mixing type with an L/D of 24 to 1.
  • the compression ratio for the mixing screw is 3.5:1.
  • the screw speed is 25 to 30 rpm.
  • a 1.21 inch diameter die with a 25 mil die gap is used.
  • the air ring is a Killion single-lip, No. 2 type.
  • Blowing conditions can be characterized by the blow up ratio, (BUR), which is the ratio of the bubble diameter to die the die diameter which gives an indication of hoop or transverse direction, (TD), stretch, or the draw-down ratio, (DDR), which is an indication of the axial or machined direction, (MD), stretch.
  • BUR blow up ratio
  • TD hoop or transverse direction
  • DDR draw-down ratio
  • Bilayer films are produced on a 10 inch, two layer, Streamlined
  • Layer configuration of the die is as follows from outside to inside layers of the die, A/B. Two 3 Vz inch David Standard extruders fed the A and B layers. The process line further utilizes a Brampton Engineering rotating air ring for polymer cooling.
  • Layer A contains a polymer prepared as described in Example 15, except at a larger scale.
  • Layer B contains a polymer prepared as described in Example 34, except at a larger scale. Both polymers are dried in a dehumidified dryer at 60 C.
  • the operation is tailored to provide the layer ratios for the films noted below in Table 12 as percentages of the total film.
  • the thickness of the film is about 2.25 mil (0.00225 inch).
  • the processing conditions for the film are provided in Table 13, below. Table 12.
  • Zone 1 195 C 160C Zone 2 220 C 165C
  • the multilayer films prepared above are converted into bags using an inline bag machine manufactured by Battenfeld Gloucester Engineering Co., Inc. downstream of the extrusion line nips.
  • the slit films are tested as fast food sandwich wraps.
  • Bilayer films are produced on a 10 inch, two layer, Streamlined Coextrusion Die, (SCD), blown film die manufactured by Brampton Engineering.
  • Layer configuration of the die is as follows from outside to inside layers of the die, A/B. Two 3 Vi inch David Standard extruders fed the A and B layers. The process line further utilizes a Brampton Engineering rotating air ring for polymer cooling.
  • Layer A contains the plasticized, starch filled polymer prepared similarly to that described for Example 106.
  • Layer B contains a polymer prepared similarly to that described for Example 7, except at a larger scale. Both polymers are dried in a dehumidified dryer at 60 C.
  • the operation is tailored to provide the layer ratios for the films noted below in Table 14 as percentages of the total film.
  • the thickness of the film is about 2.25 mil (0.00225 inch).
  • the processing conditions for the film are provided in Table 15, below.
  • Zone 1 170C 220 C Zone 2 190C 230 C Zone 3 200C 240 C Zone 4 200C 240 C Zone 5 205C 245 C
  • the multilayer films prepared above are converted into bags using an inline bag machine manufactured by Battenfeld Gloucester Engineering Co., Inc. downstream of the extrusion line nips.
  • the slit films are tested as fast food sandwich wraps.
  • the multilayer films prepared above are converted into bags using an inline bag machine manufactured by Battenfeld Gloucester Engineering Co., Inc. downstream of the extrusion line nips.
  • the slit films are tested as fast food sandwich wraps. Examples 144 - 170 And Comparative Examples CE 12 - CE 17.
  • polyester resins prepared similarly to that described in the Examples and Comparative Example listed below in Table 18, except at a larger scale, are dried in a desiccant air dryer with a dew point of - 40 C overnight at a temperature of 60 C.
  • the polyester resins are extrusion coated onto paperboard stock by feeding the dried pellets into a 2.5 inch commercial extruder having a barrel length to diameter ratio of 28:1.
  • the five zones of the extruder are maintained at a temperature in the range noted below within Table 18.
  • a single flight screw having eight compression flights, four metering flights, a two flight mixing section and six metering flights is used in the extruder.
  • the screw speed is maintained at 180 revolutions per minute, (rpm).
  • the molten polyester resins are passed through three 24 X 24 mesh screens.
  • the polymers are passed through a center fed die with 0.75 inch lands having a die opening of 36 inches by 0.02 inches.
  • the extrusion feed rate is held constant at 460 pounds per hour.
  • the resulting extrudates are passed through a 5 inch air gap into the nip formed by a rubber-covered pressure roll and a chill roll.
  • the paperboard stock noted below in Table 18, that is 32 inches wide is fed into the nip with the roll in contact with the film.
  • a nip pressure of 100 pounds per linear inch is applied.
  • a 24 inch diameter mirror finished chill roll is maintained at a temperature of 19 C during the extrusion trials.
  • the coated paperboard is taken off the chill roll at a point 180 degrees from the nip formed by the pressure roll and the chill roll.
  • the chill roll is operated at linear speeds of 300 feet per minute, to obtain a polyester resin thickness of 1.25 mils.
  • the polyester resin thickness can be modified by operational modifications.

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