US20030060596A1 - Amorphous copolyesters - Google Patents

Amorphous copolyesters Download PDF

Info

Publication number
US20030060596A1
US20030060596A1 US10/195,267 US19526702A US2003060596A1 US 20030060596 A1 US20030060596 A1 US 20030060596A1 US 19526702 A US19526702 A US 19526702A US 2003060596 A1 US2003060596 A1 US 2003060596A1
Authority
US
United States
Prior art keywords
mole percent
residues
copolyester
amorphous
terephthalic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/195,267
Other languages
English (en)
Inventor
Sam Turner
Jonathan Milburn
Robert Seymour
Kab Seo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to US10/195,267 priority Critical patent/US20030060596A1/en
Priority to EP02748213A priority patent/EP1414883B1/en
Priority to JP2003514031A priority patent/JP4299124B2/ja
Priority to KR1020047000764A priority patent/KR100891236B1/ko
Priority to DE60214734T priority patent/DE60214734T2/de
Priority to CNB028144791A priority patent/CN1239562C/zh
Priority to AT02748213T priority patent/ATE339461T1/de
Priority to PCT/US2002/023046 priority patent/WO2003008477A1/en
Priority to BR0211112-8A priority patent/BR0211112A/pt
Priority to MXPA04000525A priority patent/MXPA04000525A/es
Publication of US20030060596A1 publication Critical patent/US20030060596A1/en
Priority to US10/808,070 priority patent/US7026027B2/en
Priority to US11/360,333 priority patent/US7834127B2/en
Priority to JP2008126133A priority patent/JP2008189944A/ja
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • 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
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • 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]

Definitions

  • This invention relates to amorphous copolyesters derived from 1,4-cyclohexanedimethanol and neopentyl glycol. More particularly, this invention relates to such copolyesters that have a combination of unique properties and to shaped articles fabricated therefrom such as profile extrusions and medical equipment.
  • PETG refers to copolyesters comprising terephthalic acid residues as the diacid residue component and a diol residue component comprising up to 50 mole percent CHDM residues with the remainder EG residues.
  • PCTG refers to copolyesters comprising T residues and a diol residue component comprising greater than 50 mole percent CHDM residues with the remainder being EG residues.
  • Copolyesters comprising T residues and diol residues comprising about 20 to 70 mole percent CHDM residues and about 80 to 30 mole percent EG residues are amorphous.
  • amorphous as defined herein means a polyester that does not exhibit a substantial crystalline melting point when scanned by differential scanning calorimetry (DSC) at a rate of 20° C./minute.
  • Amorphous copolyesters in general possess a combination of desirable properties for many applications. These properties include excellent clarity and color, toughness, ease of processing, and chemical resistance. Accordingly, amorphous copolyesters are known to be useful for the manufacture of extruded sheet, packaging materials, and parts for medical devices, etc. Application in transparent medical parts requires resistance to craze formation and mechanical failure when exposed to lipid and/or isopropyl alcohol (IPA) solutions. Whereas amorphous copolyesters are known in the art to have good resistance to these chemicals and are widely applied in these applications, craze formation occurs at high strains and is thus an area of needed improvement. Consequently, there is an unmet need for amorphous copolyesters that under high strains have improved resistance to lipid and IPA solutions.
  • IPA isopropyl alcohol
  • Neopentyl glycol (NPG-2,2-dimethylpropane-1,3-diol) has been used in combination with EG and terephthalic acid to form amorphous copolyesters.
  • NPG and CHDM as the diol component of copolyesters has received minimal attention.
  • Several early references disclose copolyesters comprising both CHDM and NPG residues and terephthalic acid residues.
  • Example 46 of U.S. Pat. No. 2,901,466 describes a copolyester of unknown composition that was reported to have a crystalline melting point of 289-297° C.
  • 3,592,875 discloses copolyester compositions that contain both NPG and CHDM residues with an added polyol present for branching.
  • U.S. Pat. No. 3,592,876 discloses polyester compositions that contain EG, CHDM and NPG residues with the NPG residue level limited to up to 10 mole percent.
  • U.S. Pat. No. 4,471,108 discloses low molecular weight polyesters some of which contain CHDM and NPG residues, but also contain a multifunctional branching agent.
  • U.S. Pat. No. 4,520,188 describes low molecular weight copolyesters comprising mixtures of aliphatic and aromatic acid residues with both NPG and CHDM residues present.
  • Japanese Patent Publication JP 3225982 B2 discloses amorphous copolyesters which are said to be useful in the formulation of coating compositions for steel sheet.
  • the disclosed copolyesters comprise a diacid component comprising mixtures of aliphatic and aromatic acid residues and a diol component comprising NPG and CHDM residues present.
  • amorphous polyesters derived from terephthalic acid, CHDM and NPG are valuable compositions useful for the manufacture of medical devices that exhibit improved resistance to degradation upon exposure to lipids.
  • the amorphous copolyesters provided by the present invention have an inherent viscosity (IV) of at least about 0.4 dL/g measured at a temperature of 25° C. at 0.25 g/dl concentration in a solvent mixture of symmetric tetrachloroethane and phenol having a weight ratio of symmetric tetrachloroethane to phenol of 2:3 and comprise:
  • a diacid component consisting essentially of about 90 to 100 mole percent terephthalic acid residues and 0 to about 10 mole percent isophthalic acid residues;
  • a diol component consisting essentially of about 10 to 70 mole percent 1,4-cyclohexanedimethanol residues and about 90 to 30 mole percent neopentyl glycol residues;
  • amorphous copolyesters comprises 100 mole percent diacid component and 100 mole percent diol component.
  • Another embodiment of the present invention concerns a shaped article such as an extruded profile or an extruded or injection molded medical device having improved resistance to degradation from exposure to lipids wherein the medical device is fabricated or prepared from an amorphous copolyester having an inherent viscosity (IV) of at least about 0.4 dL/g measured at a temperature of 25° C. at 0.25 g/dl concentration in a solvent mixture of symmetric tetrachloroethane and phenol having a weight ratio of symmetric tetrachloroethane to phenol of 2:3 and comprising:
  • IV inherent viscosity
  • a diacid component consisting essentially of about 90 to 100 mole percent terephthalic acid residues and 0 to about 10 mole percent isophthalic acid residues;
  • a diol component consisting essentially of about 10 to 70 mole percent 1,4-cyclohexanedimethanol residues and about 90 to 30 mole percent neopentyl glycol residues;
  • amorphous copolyesters comprises 100 mole percent diacid component and 100 mole percent diol component.
  • a method of melt processing an amorphous copolyester having a moisture content prior to melt processing of 0.02 weight % or more comprises the steps of:
  • a diacid component consisting essentially of about 90 to 100 mole percent terephthalic acid residues and 0 to about 10 mole percent isophthalic acid residues;
  • copolyester is based on 100 mole percent diacid component and 100 mole percent diol component.
  • FIG. 1 shows the melt viscosity shear rate curve at 260° C. for PETG, PROVISTATM, and the amorphous copolyester of the present invention described in Example 8.
  • FIG. 2 shows the melt viscosity shear rate curve at 260° C. for PETG, PROVISTATM, and the amorphous copolyester of the present invention described in Example 10.
  • Copolyesters comprising based on terephthalic acid (T) resdiues and, optionally up to about 10 mole percent isophthalic acid residues, 1,4-cyclohexane-dimethanol (CHDM) residues, and neopentyl glycol (NPG) residues are amorphous in the approximate composition ranges of 10 to 70 CHDM to 90 to 30 NPG and these unique amorphous copolyesters show surprising improved resistance to crazing when exposed to lipids or IPA.
  • T terephthalic acid
  • CHDM 1,4-cyclohexane-dimethanol
  • NPG neopentyl glycol
  • the combination of CHDM and NPG as comonomer diols in the copolyesters of the present invention results in copolyester backbones that exhibit enhanced stability to hydrolysis for the amorphous composition range.
  • the present copolyesters having sufficient molecular weight to be molding or extrusion grade plastics and based solely on CHDM and NPG as diols, are not known.
  • it is unexpected that the addition of NPG to a copolyester would improve resistance to lipids and IPA.
  • the amorphous copolyesters of the present invention may be prepared by conventional polymerization processes known in the art, such as the procedures disclosed in U.S. Pat. Nos. 4,093,603 and 5,681,918.
  • polycondensation processes useful in the present invention include melt phase processes conducted with the introduction of an inert gas stream, such as nitrogen, to shift the equilibrium and advance to high molecular weight or the more conventional vacuum melt phase polycondensations, at temperatures in the range of from about 240 to 300° C. or higher which are practiced commercially.
  • the terephthalic and isophthalic acid residues of the copolyesters may be derived from either the dicarboxylic acids or ester-producing equivalents thereof such as esters, e.g., dimethyl terephthalate and dimethyl isophthalate, or acid halides, e.g. acid chlorides.
  • esters e.g., dimethyl terephthalate and dimethyl isophthalate
  • acid halides e.g. acid chlorides
  • conventional additives may be added to the copolyesters of the invention in typical amounts. Examples of such additives include pigments, colorants, stabilizers, antioxidants, extrusion aids, slip agents, carbon black, flame retardants and mixtures thereof.
  • the polymerization reaction may be carried out in the presence of one or more conventional polymerization catalysts.
  • Typical catalysts or catalyst systems for polyester condensation are well-known in the art. Suitable catalysts are disclosed, for Example, in U.S. Pat. Nos. 4,025,492,4,136,089, 4,176,224, 4,238,593, and 4,208,527, the disclosures of which are herein incorporated by reference. Further, R. E. Wilfong, Journal of Polymer Science, 54, 385 (1961) describes typical catalysts, which are useful in polyester condensation reactions.
  • Preferred catalyst systems include Ti, Ti/P, Mn/Ti/Co/P, Mn/Ti/P, Zn/Ti/Co/P, Zn/Al.
  • copolymerizable toners When cobalt is not used in the polycondensation, copolymerizable toners may be incorporated into the copolyesters to control the color of these amorphous copolyesters so that they are suitable for the intended applications where color may be an important property.
  • other additives such as antioxidants, dyes, etc. may be used in the copolyesterifications.
  • the copolyesters of the invention have an inherent viscosity (IV) of at least about 0.4 dL/g, preferably about 0.5 to 1.1 dL/g, measured at a temperature of 25° C. at 0.25 g/dl concentration in a solvent mixture of symmetric tetrachloroethane and phenol having a weight ratio of symmetric tetrachloroethane to phenol of 2:3.
  • the diacid component consists essentially of at least 95 mole percent and more preferably 100 mole percent terephthalic acid.
  • the diol component preferably consists of residues of about 30 to 70 mole percent CHDM residues and about 70 to 30 mole percent NPG residues.
  • the most preferred copolyesters have an IV of about 0.60 to 1.1 dL/g and comprise:
  • amorphous copolyesters comprises 100 mole percent diacid component and 100 mole percent diol component.
  • the copolyesters of the invention can be molded and extruded using conventional melt processing techniques to produce the shaped article of our invention.
  • the copolyesters are particularly useful in the manufacture of small and intricately shaped articles such as tubing used for handling and transporting medical fluids, etc.
  • the lipid resistance of the copolyesters of our invention under external strain renders the copolyesters particularly useful in the manufacture of shaped articles including medical devices such as tubes, pump housings, connectors, etc. where lipid resistance is important.
  • Such shaped articles manufactured from the copolyesters of this invention possess improved resistance to degradation by medical lipid solutions such as Liposyn II 20% intraveneous fat emulsion.
  • the improved resistance to degradation is manifested by retention of elongation to break values (retention of toughness) and significant reduction of visual crazing in molded test bars as shown in the examples below.
  • the shaped articles may be produced according to conventional thermoplastic processing procedures such as injection molding, calendaring, extrusion and rotational molding.
  • the amorphous copolyesters of the present invention derived from CHDM and NPG exhibit improved hydrolytic stability at various melt temperatures.
  • the moisture content of the copolyester typically is reduced to less than about 0.02% prior to melt processing.
  • the minimal drying is performed by conventional methods for less than 2 hours at 60 to 100° C.
  • a desiccant bed with forced dehumidified air at 60° C. to 100° C. is preferred. Even more preferably, there is no drying of the copolyester prior to melt processing.
  • the melt viscosity versus shear rate relationship in polymers is a very important property of polymeric materials.
  • One useful melt viscosity/shear rate relationship is shear thinning. Shear thinning occurs when the melt flow is non-Newtonian and shows a reversible decrease in viscosity with increasing shear rate. Shear thinning characteristics are very important for allowing the processing of injection molded and extruded parts and sheets, such as profiles.
  • Profile extrusion is an extrusion process where special dies are used to produce articles of asymmetrical shapes. House siding, plastic tubes, channels, baseboard moldings, etc. are examples of profile extruded parts and are referred to as profiles.
  • amorphous polymers are used in profile extrusion to avoid the shrinking that takes place during crystallization processes.
  • the asymmetric nature of the products from this process requires special resin properties such as high melt strength at low melt viscosities and shear thinning melt rheology.
  • the amorphous copolyesters of the present invention exhibit improved shear thinning behavior.
  • FIG. 1 shows melt viscosity shear rate curves at 260° C. for several polymers: (1) PETG is a copolyester comprises a diacid component consisting of 100 mole percent terephthalic acid residues and a diol component consisting of 69 mole percent ethylene glycol residues and 31 mole percent CHDM residues and is commercially available as EASTAR® 6763 Copolyester from Eastman Chemical Company; (2) PROVISTATM copolyester (also available from Eastman Chemical Company), which is specifically designed to shear thin by adding branching agents, has a composition similar to PETG; and (3) the copolyester of Example 8 of the present invention.
  • PETG is a copolyester comprises a diacid component consisting of 100 mole percent terephthalic acid residues and a diol component consisting of 69 mole percent ethylene glycol residues and 31 mole percent CHDM residues and is commercially available as EASTAR® 6763 Copolyester from East
  • Example 8 exhibits a shear thinning behavior that resembles the PROVISTATM copolyester and not the PETG.
  • FIG. 2 shows melt viscosity shear rate curves at 260° C. for the copolyester of Example 10 which shear thins like PROVISTATM copolyester and not PETG copolyester.
  • the complex viscosity was determined by a Rheonmetrics Dynamic Analyzer (RDA II) with 25 mm diameter parallel plates, 1 mm gap and 10% strain at 260° C. The samples were dried at 60° C. for 24 hours in a vacuum oven before the frequency sweep test.
  • RDA II Rheonmetrics Dynamic Analyzer
  • another embodiment of the present invention is a profile produced by profile extrusion comprising an amorphous copolyester composition having an inherent viscosity of at least 0.5 dl/g and comprising:
  • a diacid component consisting essentially of about 90 to 100 mole percent terephthalic acid residues and 0 to about 10 mole percent isophthalic acid residues;
  • a diol component consisting essentially of about 10 to about 70 mole percent 1,4-cyclohexanedimethanol residues and about 90 to about 30 mole percent neopentyl glycol residues;
  • amorphous copolyesters comprises 100 mole percent diacid component and 100 mole percent diol component.
  • another embodiment is an injection molded article comprising an amorphous copolyester consisting essentially of an acid component of residues of at least 90 mole percent terephthalic acid and a glycol component of residues of about 10 to about 70 mole percent 1,4-cyclohexanedimethanol and about 90 to about 30 mole percent neopentyl glycol, based on 100 mole percent acid component and 100 mole percent glycol component.
  • an amorphous copolyester consisting essentially of an acid component of residues of at least 90 mole percent terephthalic acid and a glycol component of residues of about 10 to about 70 mole percent 1,4-cyclohexanedimethanol and about 90 to about 30 mole percent neopentyl glycol, based on 100 mole percent acid component and 100 mole percent glycol component.
  • the following Examples are intended to illustrate, but not limit, the scope of the present invention.
  • the inherent viscosities were measured at a temperature of 25° C. at 0.25 g/dl concentration in a solvent mixture of symmetric tetrachloroethane and phenol having a weight ratio of symmetric tetrachloroethane to phenol of 2:3.
  • the 2 nd cycle glass transition temperatures were determined according to DSC at a heating rate of 20° C./min to a temperature of 280-300° C., quenching in liquid nitrogen to 0° C., and then rerunning the sample and recording the Tg as the 2 nd cycle glass transition temperature.
  • Final copolyester compositions were determined by proton NMR analysis on a 600 MHz JEOL instrument.
  • a copolyester comprising a diacid component consisting of 100 mole percent terephthalic acid residues and a diol component consisting of 66 mole percent CHDM residues and 34 mole percent NPG residues (hereinafter referenced as 100T/85CHDM/15NPG) was prepared.
  • CHDM 46.37 g, 0.32 moles
  • 1.49 ml of a solution containing 15 g of titanium tetraisopropoxide in 250 ml of n-butanol were added to a 500 ml single-neck, round-bottom flask.
  • the flask was immersed in a Belmont metal bath that was pre-heated to 200° C. Immediately after the flask was immersed the temperature set point was increased to 220° C., and held for 1 hour. After the hour at 220° C. the temperature was increased to 260° C., and held for 30 minutes. After this time the theoretical amount of methanol was collected. The pressure in the flask then was reduced from atmospheric to 0.5 Torr. When the pressure had been reduced to 0.5 Torr the temperature set point was raised to 280° C. Stirring was reduced as the viscosity increased until a stir rate of 15 revolutions per minute (rpm) was obtained. The vacuum was discontinued and nitrogen was bled into the flask.
  • rpm revolutions per minute
  • the polymer was allowed to solidify by cooling to a temperature below Tg, removed from the flask and ground to pass through a 3 mm screen.
  • the inherent viscosity of the polymer was 0.895 dL/g.
  • the polymer had a 2 nd cycle Tg of 87.82° C.
  • Compositional analysis (by NMR) showed the diol component of the copolyester consisted of 66.1 mole percent CHDM residues and 33.9 mole percent NPG residues.
  • a copolyester having the composition 100T/61CHDM/39NPG was prepared. DMT (77.60 g, 0.40 moles), NPG 33.70 grams (0.33 moles) of NPG, 39.74 grams (0.28 moles) of CHDM, and 1.49 ml of a solution containing 15 grams of titanium tetraisopropoxide in 250 ml of n-butanol were added to a 500 ml single neck round bottom flask and reacted and polymerized according to the procedure described in Example 1. The inherent viscosity of the polymer was 0.930 dL/g. The polymer had a 2 nd cycle Tg of 86.70° C. with no crystalline melting point observed, and compositional analysis showed that the diol component of the copolyester consisted of 61.4 mole percent CHDM residues and 38.6 mole percent NPG residues.
  • a copolyester having the composition 100T/56CHDM/44NPG was prepared. DMT (77.6 g, 0.40 moles), NPG (38.48 g, 0.37 moles), CHDM (33.12 g, 0.23 moles), and 1.47 ml of a solution containing 15 g of titanium tetraisopropoxide in 250 ml of n-butanol were added to a 500 ml, single-neck, round-bottom flask and reacted and polymerized according to the procedure described in Example 1. The inherent viscosity of the polymer was 0.938 dL/g. The polymer had a 2 nd cycle Tg of 85.90° C. with no crystalline melting point observed, and compositional analysis showed that the diol component of the copolyester consisted of 55.8 mole percent CHDM and 44.2 mole percent NPG residues.
  • a copolyester having the composition 100T/45CHDM/55NPG was prepared. DMT (77.60 g, 0.4 moles), NPG (43.26 g, 0.42 moles), CHDM (26.50 g, 0.18 moles), and 1.44 ml of a solution containing 15 g of titanium tetraisopropoxide in 250 ml of n-butanol were added to a 500 ml single neck round bottom flask and reacted and polymerized according to the procedure described in Example 1. The inherent viscosity of the polymer was 0.897 dL/g. The polymer had a 2 nd cycle Tg of 83.66° C. with no crystalline melting point observed, and compositional analysis showed the diol component of the copolyester consisted of 44.7 mole percent CHDM and 55.3 mole percent NPG residues.
  • a copolyester having the composition 100T/32CHDM/68NPG was prepared. DMT (77.60 g, 0.4 moles), NPG (48.05 g, 0.46 moles), CHDM (19.87 g, 0.14 moles), and 1.42 ml of a solution containing 15 g of titanium tetraisopropoxide in 250 ml of n-butanol were added to a 500 ml single neck round bottom flask and reacted and polymerized according to the procedure described in Example 1. The inherent viscosity of the polymer was 1.143 dL/g. The polymer had a 2 nd cycle Tg of 82.43° C. with no crystalline melting point observed, and compositional analysis showed the diol component of the copolyester consisted of 32.3 mole percent CHDM and 67.7 mole percent NPG residues.
  • a copolyester having the composition 100T/21CHDM/79NPG was prepared. DMT (77.60 g, 0.4 moles), NPG (52.83 g, 0.51 moles), CHDM (13.25 g, 0.09 moles), and 1.40 ml of a solution containing 15 g of titanium tetraisopropoxide in 250 ml of n-butanol were added to a 500 ml single neck round bottom flask and reacted and polymerized according to the procedure described in Example 1. The inherent viscosity of the polymer was 0.925 dL/g. The polymer had a 2 nd cycle Tg of 80.30° C. with no crystalline melting point observed, and compositional analysis showed the diol component of the copolyester consisted of 21.4 mole percent CHDM and 78.6 mole percent NPG residues.
  • a copolyester having the composition 100T/15CHDM/85NPG was prepared. DMT (77.60 9, 0.4 moles), NPG (57.62 g, 0.55 moles), CHDM (6.62 g, 0.05 moles), and 1.37 ml of a solution containing 15 g of titanium tetraisopropoxide in 250 ml of n-butanol were added to a 500 ml single neck round bottom flask and reacted and polymerized according to the procedure described in Example 1. The inherent viscosity of the polymer was 0.863 dL/g. The polymer had a 2 nd cycle Tg of 77.78° C. with no crystalline melting point observed, and compositional analysis showed the diol component of the copolyester consisted of 14.6 mole percent CHDM and 85.4 mole percent NPG residues.
  • a copolyester having the composition 100T/67CHDM/33NPG was manufactured in a batch pilot plant reactor.
  • DMT (10.215 kg, 22.5 pounds), NPG (4.495 kg, 9.9 pounds), CHDM (5.153 kg, 11.35 pounds), and 53.4 g of a solution of titanium isopropoxide in n-butanol were charged into a 68.13 liter (18-gallon) batch reactor with intermeshing spiral agitators and a distillation column.
  • the agitators were operated forward for 50 minutes and then reversed for 10 minutes.
  • the internal temperature was increased to 200° C. and held for 2 hours.
  • the temperature then was increased to 260° C. and held for 30 minutes.
  • the weight of distillate was recorded and the temperature was increased to 280° C. Upon reaching 280° C. the weight of distillate again was recorded.
  • the agitator was changed to switch directions every 6 minutes, and vacuum was applied at a rate of 13 Torr/minute until full vacuum (0.5 Torr) was reached.
  • the polymerization mixture was mainatained for 25 minutes at 45 rpm, and then maintained for 15 minutes at 10 rpm.
  • the copolyester thus obtained then was immediately extruded and chopped into pellets.
  • the polymer had an inherent viscosity of 0.791 dL/g, and a 2 nd cycle Tg of 87.48° C. with no crystalline melting point observed.
  • a copolyester having the composition 100T/45CHDM/55NPG was produced in a batch pilot plant reactor.
  • DMT (10.669 kg, 23.5 pounds), NPG (6.220 kg, 13.7 pounds), CHDM (3.223 kg, 7.1 pounds), and 53.4 g of a solution of titanium isopropoxide in n-butanol were charged into a 68.13 liter (18-gallon) batch reactor with intermeshing spiral agitators and a distillation column. After charging the raw materials, the manufacturing procedure described in Example 10 was repeated.
  • the resulting polymer had an inherent viscosity of 0.844 dL/g, and a 2 nd cycle Tg of 84.08° C. with no crystalline melting point observed.
  • Example 9 was repeated except that the polycondensation was modified to produce a copolyester having a lower IV. After reaching full vacuum (0.5 Torr), the agitator was held at 25 rpm for only 30 minutes, and then held for 15 minutes at 10 rpm. The copolyester polymer then was immediately extruded and chopped into pellets. The copolyester polymer had an inherent viscosity of 0.713 dL/g, and a 2 nd cycle Tg of 83.41° C. with no crystalline melting point observed. Compositional analysis (by NMR) showed the diol component of the copolyester consisted of 44.1 mole percent CHDM and 55.9 mole percent NPG. The color values were as follows:
  • Copolyester III Amorphous copolyester of Example 8.
  • Copolyester IV Amorphous copolyester of Example 9.
  • Standard tensile test bars (ASTM-D638) of each of the copolyesters I, II, III, and IV were prepared by injection molding. The bars were placed on three-point-bend strain rigs at fixed strains of 0, 0.5, 1.5 and 2.7% while simultaneously being exposed to Liposyn II 20% intravenous fat emulsion (lipid solution) for 72 hours. Exposure to the lipid solution was accomplished by placing a 2.54 mm ⁇ 1.77 mm (1 inch ⁇ 0.5 inch) patch of filter paper over the center of the bar and saturating the patch with the lipid solution initially and then rewetting several times a day. The treated bars were then subjected to tensile testing according to ASTM D638.
  • a copolyester having the composition 100T/64CHDM/36NPG was produced in a batch pilot plant reactor.
  • DMT (10.215 kg, 22.5 pounds), NPG (4.495 kg, 9.9 pounds), CHDM (5.153 kg, 11.35 pounds), and 53.4 grams of a solution of titanium isopropoxide in n-butanol were charged into a 68.13 liter (18-gallon) batch reactor with intermeshing spiral agitators and a distillation column.
  • the agitator was operated forward for 50 minutes and then reversed for 10 minutes.
  • the internal temperature was increased to 200° C. and held for 2 hours.
  • the temperature was then increased to 260° C. and maintained for 30 minutes.
  • a copolyester having the composition 100T/38CHDM/62NPG was produced in a batch pilot plant reactor.
  • DMT (10.669 kg, 23.5 pounds), NPG (6.220, 13.7 pounds), CHDM (3.223, 7.1 pounds), and 53.4 grams of a solution of titanium isopropoxide in n-butanol were charged into a 68.13 liter (18-gallon) batch reactor with intermeshing spiral agitators and a distillation column.
  • the agitator was operated forward for 50 minutes and then reversed for 10 minutes.
  • the internal temperature was increased to 200° C. and maintained for 2 hours.
  • the temperature was then increased to 260° C. and maintained for 30 minutes.
  • the procedure used in determining loss in molecular weight as a result of hydrolysis involved placing a sample of the copolyester into the barrel of a capillary rheometer and then heating to either 250° C. or 280° C. and holding for the specified time. The sample was removed, after this treatment, and the molecular weight was determined by standard size exclusion chromatography. The molecular weight loss was calculated from the equation 1 ⁇ M w /M o where M w is the molecular weight after treatment and M o is the original molecular weight. The higher the number the greater the weight loss.
  • the values listed in the “hydrolysis” rows are undried samples, while those listed in the “thermal” rows refer to samples dried at 60° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Materials For Medical Uses (AREA)
  • Infusion, Injection, And Reservoir Apparatuses (AREA)
  • External Artificial Organs (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
US10/195,267 2001-07-18 2002-07-15 Amorphous copolyesters Abandoned US20030060596A1 (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
US10/195,267 US20030060596A1 (en) 2001-07-18 2002-07-15 Amorphous copolyesters
PCT/US2002/023046 WO2003008477A1 (en) 2001-07-18 2002-07-18 Amorphous copolyesters
BR0211112-8A BR0211112A (pt) 2001-07-18 2002-07-18 Copoliéster amorfo, artigo conformado, artigo médico para contactar soluções contendo lipìdios, método para processamento em fusão de um copoliéster amorfo, perfil produzido por extrusão de perfil, e, artigo moldado por injeção
KR1020047000764A KR100891236B1 (ko) 2001-07-18 2002-07-18 비결정성 코폴리에스테르
DE60214734T DE60214734T2 (de) 2001-07-18 2002-07-18 Amorphe copolyester
CNB028144791A CN1239562C (zh) 2001-07-18 2002-07-18 无定形的共聚酯
AT02748213T ATE339461T1 (de) 2001-07-18 2002-07-18 Amorphe copolyester
EP02748213A EP1414883B1 (en) 2001-07-18 2002-07-18 Amorphous copolyesters
JP2003514031A JP4299124B2 (ja) 2001-07-18 2002-07-18 非晶質コポリエステル
MXPA04000525A MXPA04000525A (es) 2001-07-18 2002-07-18 Copoliesteres amorfos.
US10/808,070 US7026027B2 (en) 2001-07-18 2004-03-24 Amorphous copolyesters
US11/360,333 US7834127B2 (en) 2001-07-18 2006-02-23 Amorphous copolyesters
JP2008126133A JP2008189944A (ja) 2001-07-18 2008-05-13 非晶質コポリエステルの造形品

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US30622101P 2001-07-18 2001-07-18
US10/195,267 US20030060596A1 (en) 2001-07-18 2002-07-15 Amorphous copolyesters

Related Child Applications (3)

Application Number Title Priority Date Filing Date
US10743112 Continuation-In-Part
US74311203A Continuation-In-Part 2001-07-18 2003-12-22
US10/808,070 Continuation-In-Part US7026027B2 (en) 2001-07-18 2004-03-24 Amorphous copolyesters

Publications (1)

Publication Number Publication Date
US20030060596A1 true US20030060596A1 (en) 2003-03-27

Family

ID=26890850

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/195,267 Abandoned US20030060596A1 (en) 2001-07-18 2002-07-15 Amorphous copolyesters
US10/808,070 Expired - Lifetime US7026027B2 (en) 2001-07-18 2004-03-24 Amorphous copolyesters

Family Applications After (1)

Application Number Title Priority Date Filing Date
US10/808,070 Expired - Lifetime US7026027B2 (en) 2001-07-18 2004-03-24 Amorphous copolyesters

Country Status (10)

Country Link
US (2) US20030060596A1 (ko)
EP (1) EP1414883B1 (ko)
JP (2) JP4299124B2 (ko)
KR (1) KR100891236B1 (ko)
CN (1) CN1239562C (ko)
AT (1) ATE339461T1 (ko)
BR (1) BR0211112A (ko)
DE (1) DE60214734T2 (ko)
MX (1) MXPA04000525A (ko)
WO (1) WO2003008477A1 (ko)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7772362B2 (en) 2007-07-16 2010-08-10 Texas State University Treatment method for imparting self-healing and shape memory properties to certain CBDO copolymers
EP2227512A1 (en) * 2007-12-18 2010-09-15 Lumimove, Inc., Dba Crosslink Flexible electroluminescent devices and systems
US8604138B2 (en) * 2008-01-14 2013-12-10 Eastman Chemical Company Extrusion blow molded articles
US9681771B2 (en) 2012-03-09 2017-06-20 Precidio Design Inc. Container for liquids
US9516974B2 (en) 2012-03-09 2016-12-13 Precidio Design Inc. Container for liquids and set for making the same
US10767005B2 (en) 2015-12-22 2020-09-08 Exxonmobil Chemical Patents Inc. Bibenzoate copolyesters and methods to produce them
US10287402B2 (en) 2016-04-29 2019-05-14 Exxonmobil Chemical Patents Inc. Polycarbonate-polyolefin block copolymers and methods of making them
WO2018097909A1 (en) 2016-11-23 2018-05-31 Exxonmobil Chemical Patents Inc. Bibenzoate copolyesters
US11999141B2 (en) 2017-05-31 2024-06-04 Bay Materials, Llc. Dual shell dental appliance and material constructions
CN115476563A (zh) 2017-05-31 2022-12-16 贝伊材料有限责任公司 双壳牙科器具和材料构造
TWI836276B (zh) * 2020-10-07 2024-03-21 美商朋瑟美國公司 聚酯系熱收縮膜

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE592181A (ko) * 1955-12-22
DE1769035A1 (de) * 1968-03-23 1971-10-07 Hoechst Ag Thermoplastische Polyesterformmassen
DE1770043A1 (de) * 1968-03-23 1971-09-23 Hoechst Ag Thermoplastische Polyester enthaltende Formmassen
DE2431072C3 (de) * 1974-06-28 1980-04-30 Bayer Ag, 5090 Leverkusen Thermoplastische Copolyester und Verfahren zu ihrer Herstellung
US4136089A (en) * 1975-02-22 1979-01-23 Bayer Aktiengesellschaft Molded articles of crystalline poly (ethylene/alkylene) terephthalates which crystallize rapidly
DE2559290B2 (de) * 1975-12-31 1979-08-02 Davy International Ag, 6000 Frankfurt Verfahren zur kontinuierlichen Herstellung von hochmolekularem PoIyäthylenterephthalat
US4093603A (en) * 1977-01-19 1978-06-06 Eastman Kodak Company Copolyesters of terephthalic acid, 1,2-propanediol and 1,4-cyclohexanedimethanol
DE2715932A1 (de) * 1977-04-09 1978-10-19 Bayer Ag Schnellkristallisierende poly(aethylen/alkylen)-terephthalate
DE2811982A1 (de) * 1978-03-18 1979-09-27 Huels Chemische Werke Ag Verfahren zur herstellung von hochmolekularem poly(ethylenterephthalat)
US4161579A (en) * 1978-04-10 1979-07-17 Celanese Corporation Extrusion grade polyethylene terephthalate
US4182841A (en) * 1978-06-12 1980-01-08 The Goodyear Tire & Rubber Company Composition of copolyesters
US4219527A (en) * 1978-10-31 1980-08-26 Celanese Corporation Extrusion grade polyethylene terephthalate
US4234708A (en) * 1979-04-23 1980-11-18 Celanese Corporation Extrusion grade polyethylene iso/terephthalate copolymer
US4238593B1 (en) * 1979-06-12 1994-03-22 Goodyear Tire & Rubber Method for production of a high molecular weight polyester prepared from a prepolymer polyester having an optional carboxyl content
US4398022A (en) * 1980-09-02 1983-08-09 Eastman Kodak Company Extrusion blow moldable copolyesters
JPS5866947A (ja) 1981-10-16 1983-04-21 Mita Ind Co Ltd 電子写真用感光体
NL8204205A (nl) * 1982-10-29 1984-05-16 Dsm Resins Bv Polyester en de toepassing daarvan in poederlak.
US4520188A (en) * 1984-09-13 1985-05-28 Whittaker Corporation Polyester-forming composition for coil coatings, improved polyester resin and method of making same
US4656715A (en) 1986-07-11 1987-04-14 Diaz Eusebio M Transmission clutch housing removal tool set
US5095089A (en) * 1988-12-28 1992-03-10 Mitsubishi Rayon Company, Ltd. Polyester copolymer
US4983711A (en) * 1989-12-04 1991-01-08 Eastman Kodak Company Copolyesters and articles extrusion blow-molded therefrom
US5145742A (en) * 1990-08-03 1992-09-08 Eastman Kodak Company Polymer pellet configuration for solid-state polymerization
DE4125167A1 (de) * 1991-07-30 1993-02-04 Zimmer Ag Modifiziertes co-polyethylenterephthalat
JP3225982B2 (ja) 1993-04-28 2001-11-05 東亞合成株式会社 鋼板塗料用共重合ポリエステル樹脂
US5376735A (en) * 1993-07-12 1994-12-27 Eastman Chemical Company Preparation of branched polyethylene terephthalate
US5849846A (en) * 1994-07-25 1998-12-15 Advanced Cardiovascular Systems, Inc. Balloons for medical catheters
US5442036A (en) * 1994-09-06 1995-08-15 Eastman Chemical Company Branched copolyesters especially suitable for extrusion blow molding
DE69531249T2 (de) * 1995-12-29 2004-05-27 Denco Inc., Wilmington Schläuche aus mit Ionomer modifiziertem Polyetherester zum Transport von medizinischen und ähnlichen Flüssigkeiten
TW381104B (en) * 1996-02-20 2000-02-01 Eastman Chem Co Process for preparing copolyesters of terephthalic acid, ethylene glycol, and 1,4-cyclohexanedimethanol
US5656715A (en) * 1996-06-26 1997-08-12 Eastman Chemical Company Copolyesters based on 1,4-cyclohexanedimethanol having improved stability
BE1010712A3 (fr) * 1996-10-25 1998-12-01 Ucb Sa Compositions en poudre a base de polyesters semi-cristallins et de polyesters amorphes, contenant des groupes methacrylyle terminaux.
US6183848B1 (en) * 1999-06-03 2001-02-06 Eastman Chemical Company Low melt viscosity amorphous copolyesters with enhanced glass transition temperatures having improved gas barrier properties

Also Published As

Publication number Publication date
JP2004536187A (ja) 2004-12-02
EP1414883B1 (en) 2006-09-13
KR100891236B1 (ko) 2009-04-01
DE60214734D1 (en) 2006-10-26
MXPA04000525A (es) 2004-05-04
US20050070686A1 (en) 2005-03-31
JP2008189944A (ja) 2008-08-21
WO2003008477A1 (en) 2003-01-30
EP1414883A1 (en) 2004-05-06
JP4299124B2 (ja) 2009-07-22
US7026027B2 (en) 2006-04-11
CN1239562C (zh) 2006-02-01
BR0211112A (pt) 2004-06-22
KR20040030813A (ko) 2004-04-09
CN1533409A (zh) 2004-09-29
ATE339461T1 (de) 2006-10-15
DE60214734T2 (de) 2007-09-13

Similar Documents

Publication Publication Date Title
US6287656B1 (en) Low melt viscosity amorphous copolyesters having improved resistance to lipids
KR101989045B1 (ko) 내후성 및 저장안정성이 우수한 생분해성 수지 조성물 및 그 제조방법
EP1185575B1 (en) Low melt viscosity amorphous copolyesters with enhanced glass transition temperatures
KR101226312B1 (ko) 가소화된 폴리에스테르로부터 제조된 필름
US6183848B1 (en) Low melt viscosity amorphous copolyesters with enhanced glass transition temperatures having improved gas barrier properties
JP2008189944A (ja) 非晶質コポリエステルの造形品
KR101796764B1 (ko) 공중합 폴리에스테르 수지 조성물 및 그 제조방법
KR20210037267A (ko) 폴리에스테르 수지 혼합물, 폴리에스테르 필름 및 이의 제조 방법
US7834127B2 (en) Amorphous copolyesters
US6924349B2 (en) Copolyester resin and articles using the same
KR950009483B1 (ko) 용융시 높은 열안정성을 가지는 성형용 폴리알킬렌 테레프탈레이트수지 및 그 성형품
JP2021155497A (ja) ポリエステル樹脂
US20120126454A1 (en) Block copolymers comprising poly(1,3-trimethylene terephthalate) and poly(1,3-trimethylene 2,6-naphthalate)
JP4152767B2 (ja) ポリエステルブロック共重合体及びその製造方法
EP4023697A1 (en) Polyester composition, its preparation method, and polyester composition film comprising the same
KR100276105B1 (ko) 열안정성 및 색상이 우수한 폴리트리메틸렌 테레프탈레이트의제조방법
EP3956380B1 (en) Processes for preparing copolyesters suitable for use in food contact applications
CN115536819B (zh) 一种高可加工性对苯二甲酸共聚酯及其制备方法
KR20210067082A (ko) 투명성 및 열적 특성이 개선된 폴리에스테르 및 그 제조방법
KR20210058574A (ko) 폐 폴리에틸렌 테레프탈레이트를 이용한 투명성 및 내화학성이 향상된 폴리에스테르의 제조방법
BR112019017619B1 (pt) Processo, polímero de poli (furandicarboxilato de trimetileno), copolímero e método para aumentar a taxa de policondensação
JPH07179588A (ja) 共重合ポリエステル及びその製造方法
JPH07179587A (ja) ポリエステル樹脂及びその製造方法
JPH1045907A (ja) ポリエステルアミド系共重合体の製造方法

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO PAY ISSUE FEE