WO1989007124A1 - Melanges de poly(etheresters) et de polyesters, et articles ainsi obtenus - Google Patents

Melanges de poly(etheresters) et de polyesters, et articles ainsi obtenus Download PDF

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Publication number
WO1989007124A1
WO1989007124A1 PCT/US1989/000378 US8900378W WO8907124A1 WO 1989007124 A1 WO1989007124 A1 WO 1989007124A1 US 8900378 W US8900378 W US 8900378W WO 8907124 A1 WO8907124 A1 WO 8907124A1
Authority
WO
WIPO (PCT)
Prior art keywords
poly
mol
recurring units
glycol
etherester
Prior art date
Application number
PCT/US1989/000378
Other languages
English (en)
Inventor
Robert William Seymour
Thomas Eduard Flora
Original Assignee
Eastman Kodak Company
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
Priority claimed from US07/151,727 external-priority patent/US4904748A/en
Application filed by Eastman Kodak Company filed Critical Eastman Kodak Company
Priority to BR898907218A priority Critical patent/BR8907218A/pt
Priority to AU31921/89A priority patent/AU618793B2/en
Publication of WO1989007124A1 publication Critical patent/WO1989007124A1/fr

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Classifications

    • 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
    • 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

Definitions

  • This invention relates to blends of flexible poly(etheresters) and rigid polyesters having unexpected levels of stiffness and notched Izod impact strength when compared with these properties of the poly(etherester) alone. This invention further relates to articles made from such blends.
  • a particular advantage of the blends of the present invention is in their use in forming sheet material to be used as a carrier for decorative and/or protective coatings.
  • the present invention provides sheet material which can be securely bonded to substrate panels to provide the protective and decorative coating as disclosed in the patent mentioned above.
  • the present invention is an improvement in that it provides desirable physical properties to the sheet material, particularly improved stiffness and impact strength.
  • the sheet material have good impact strength, especially in parts such as bumpers, so that permanent indentations and/or fractures will not occur when struck by hard objects.
  • the present invention provides blends of poly(etherester) and polyesters which are especially useful in formation of the carrier sheet referred to above due to the improved properties of stiffness and impact strength.
  • Figure 1 is a cross section of a finished structure utilizing a carrier sheet of the blend according to the present invention.
  • blends according to this invention are particularly useful in thermoforming processes, where the blends are first formed into a sheet and subsequently thermoformed by the application of heat and pressure, using conventional well known techniques, to form the finished article. Also, the presence of the relatively rigid polyester (a less crystalline polymer) in the blend makes the blend more easily thermoformed.
  • the blends are also useful in conventional injection molding and extrusion applications. According to the present invention, there are provided blends of a flexible poly(etherester) with a more rigid polyester, the blends characterized by containing (A) 98-2 weight % of a flexible poly(etherester) having an I.V. of 0.8—1.5 and recurring units from
  • a dicarboxylic acid component consisting essentially of 1,4—cyclohexanedicarbox lie acid having a trans isomer content of at least 70%
  • poly(oxytetra— methylene) glycol having a molecular weight of 500 to 1100
  • 2-98 weight % of a relatively rigid polyester having recurring units from 80—100 mol % terephthalic acid and at least one aliphatic or cycloaliphatic glycol having 2—12 carbon atoms, said polyester having an I.V. of 0.5-1.0, the blends having improved stiffness when compared to the poly(etherester) alone.
  • the blends have unexpectedly improved notched Izod impact strengths when compared to the poly(etherester) alone when the blends contain 98-60 wt % of the flexible poly(esterether) and 2—40 wt % of the relatively rigid polyester.
  • the dibasic acid component of the poly(esterether) of this invention consists essentially of 1,4—cyclohexanedicarboxylic acid having a trans isomer content of at least 70%, preferably at least 80% and most preferably at least 85% trans isomer content.
  • 1,4 Cyclohexanedicarboxylic acid and
  • 1,4—cyclohexanedimethanol are well known in the art and commercially available.
  • "Man-Made Fibers: Science and Technology” Vol. Ill, edited by Mark, Atlas and Cernia, published by Interscience Publishers describes preparation of 1,4—cyclohexanedicarboxylic acid and 1,4—cyclohexanedimethanol at page 85.
  • the poly(oxytetramethylene) glycol component of this invention is commercially available, and is prepared by well known techniques.
  • the poly(oxytetramethylene) glycol has a molecular weight of between 500 and 1100, preferably 1000 (weight average). It is used in an amount of from 5 to 35 mol %, preferably 8—15%, based on the total glycol mol %.
  • the poly(esterether) of this invention further may comprise up to 1.5 mol %, based on the acid or glycol component, of a polybasic acid or polyhydric alcohol branching agent having at least three COOH or OH functional groups and from 3 to 60 carbon atoms. Esters of many such acids or polyols may also be used. Suitable branching agents include trimellitic acid or anhydride, trimesic acid, trimethylol ethane, trimethylol propane, and trimer acid.
  • the total acid reactants should be 100 mol %, and the total glycol reactants should be 100 mol %.
  • the acid reactant is said to "consist essentially of” 1.4—cyclohexanedicarboxylic acid, if the branching agent is a polybasic acid or anhydride, it will be calculated as part of the 100 mol % acid.
  • the glycol reactant is said to "consist essentially of" 1,4—cyclohexanedimethanol and poly(oxytetra— methylene) glycol, if the branching agent is a polyol, it will be calculated as part of the 100 mol- % glycol.
  • the poly(esterethers) of this invention preferably include a phenolic antioxidant. It is preferred that the phenolic antioxidant be hindered and relatively non—volatile. Tetrakis[methylene— (3,5-di—tert—butyl— -hydroxyhydrocinnamate)methane] which is commercially available from Geigy Chemical Company as Irganox 1010 antioxidant, is preferred. Preferably, the antioxidant is used in an amount of from 0.1 to 1.0, based on the weight of copolyester— ether.
  • trans and cis isomer contents of the final copolyesterether are controlled in order to give polymers that setup or crystallize rapidly.
  • Cis and trans isomer contents are measured by conventional methods well known to those skilled in the art. See, for example, U.S. Patent No. 4,349,469.
  • the poly(etherester) used in this invention may be prepared by conventional techniques. See, for example, U.S. Patent No. 4,349,469.
  • the polyester used in this invention may be prepared by conventional techniques using an acid component consisting essentially of terephthalic acid. Minor amounts of other conventionally used dicarboxylic acids (up to 10%) such as isophthalic, naphthalene dicarboxylic or aliphatic dicarboxylic acids having 4 to 12 carbon atoms may be used.
  • Conventional glycols, or combinations of glycols for copolymers, having 2 to 12 carbon atoms may be used.
  • the preferred glycols are ethylene glycol, 1,4—butanediol and 1,4—cyclohexanedimethanol, and combinations thereof.
  • glycols are ethylene glycol and 1,4—cyclohexanedimethanol and combinations thereof.
  • the I.V. of the polyester is * .5-1.0.
  • the flexible ⁇ oly(etherester) and rigid polyester may be combined by conventional plastic melt-mixing methods such as, for example, melt blending using an extruder.
  • the blends are useful in injection molded articles, such as fascia and tubing, and sheet material for thermoformed articles.
  • the sheet material made from the blends described above may be used in the manner shown in Figure 1.
  • the carrier sheet is produced from the blends described above. It is first provided with a decorative and/or protective coating, which may conveniently be a suitable point.
  • the optional topcoat which may be used as a protective coating or to provide glass, may be used if desired.
  • the coatings may be applied by conventional means known to those skilled in the art.
  • Upon formation of the layered sheet material it may be applied to a substrate panel by in—mold processing or simple bonding as described hereinbefore. If desired, and depending on the composition of the substrate, an adhesive or tie layer may be used to facilitate the bond.
  • Polymer "Z" is described-as a polyester having an I.V. of 0.75 and recurring units from
  • Example 1 Polymer X is blended in varying ratios with Polymer Y by mixing pellets then compounding on a single screw extruder. The resulting blend is injection molded into bars for testing. Surprisingly, it was found that the flexural modulus, measured according to ASTM D790, of the blends was higher than the expected values. It may be observed that the values actually obtained on the blends are above the expected values.
  • the flexible p ⁇ lyetherester is Polymer X
  • the relatively rigid polyester is polyethylene terephthalate having an I.V. of 0.70.
  • Example 4 Flexible polyetheresters are blended with relatively rigid polyesters as indicated in the following table, and the flexural modulus is measured.
  • the flexible polyetherester is Polymer X and the relatively rigid polyester is a polyester of terephthalic acid, 68 mol % 1,4—cyclohexanedimethanol and 32 mol % ethylene glycol having an I.V. of 0.75.
  • Example 5 Flexible polyetheresters are blended with relatively rigid polyesters as shown in the following table and properties are measured.
  • the flexible polyetherester is the same as Polymer X, except the trimellitic anhydride is omitted.
  • the relatively rigid polyester is Polymer Y.
  • the data shown in parentheses is the predicted value for comparison, showing the modulus of the blends according to this invention being higher than expected.
  • Example 6 Flexible polyetheresters are blended with relatively rigid polyesters as shown in the following table and properties are measured.
  • the flexible polyetherester is the same as Polymer X, except the concentration of 1,4—cyclohexanedimethanol is 70 mol % and the concentration of the poly(oxytetramethylene glycol) is 30 mol %.
  • the relatively rigid polyester is Polyester Y. % Flexible % Flexural Modulus* Notched Izod Polyether— Polymer ( ) Indicates Joules/ ester Y Predicted Value ft-lb/in. Meter
  • Example 7 Example 6 is repeated, except the concentration of 1,4—cyclohexanedimethanol is 80 mol % and the concentration of poly(oxytetramethylene glycol) is 20 mol %.
  • Example 10 Each of the polymer blends described above is extruded into a sheet, provided with a paint layer by roll coating, and allowed to dry. The sheet is then provided with a suitable adhesive on the side opposite the paint and bonded to a panel by a thermoforming technique. During the thermoforming operation, the sheet is first heated to a soft state and air pressure differential used to draw the soft sheet around a support panel of polypropylene. The experiments are repeated, using the in-m ⁇ ld processing technique described hereinbefore. In these experiments, it is seen that the stiffness of the carrier sheet is compatible with that of the support panel.
  • the impact resistance (values of which are set forth in the above examples) is adequate for uses such as automobile bumpers where crack resistance, indentation resistance and energy absorption is important.
  • additives may be used in either component or the blend.
  • additives include colorants, stabilizers, plasticizers, flame retardants, adhesive promoters, etc.
  • the inherent viscosity is measured at 25°C using 0.50 gram of copolyester per 100 ml of a solvent consisting of 60 percent by weight phenol and 40 percent by weight tetrachloroethane.
  • the Flexural Modulus and notched Izod impact strength tests used herein are in accordance with ASTM D790 and ASTM D256 respectively.

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  • 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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Compositions comprenant un mélange de (A) 98-2 % en poids d'un poly(étherester) souple présentant des unités récurrentes provenant d'un acide dicarboxylique de 1,4-cyclohexane possédant une teneur en isomères trans d'au moins 70 %, un constituant glycol composé essentiellement de 1,4-cyclohexanediméthanol et de poly(oxytétraméthylène) glycol, (B) 2-98 % en poids d'un polyester relativement rigide, ces mélanges ayant une rigidité et une résilience selon Izod améliorées par rapport au poly(étherester) seul. Sont également décrits des matériaux en feuille adaptés pour être collés sur un substrat, lesdits matériaux comportant une feuille support du mélange précité, présentant sur une face un revêtement décoratif et/ou protecteur.
PCT/US1989/000378 1988-02-03 1989-01-31 Melanges de poly(etheresters) et de polyesters, et articles ainsi obtenus WO1989007124A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
BR898907218A BR8907218A (pt) 1988-02-03 1989-01-31 Composicao que compreende uma mistura de um poli-eter-ester flexivel com um poliester mais rigido,artigo moldado,material laminado e substrato
AU31921/89A AU618793B2 (en) 1988-02-03 1989-01-31 Blends of poly(etheresters) and polyesters and articles made therefrom

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US151,727 1988-02-03
US07/151,727 US4904748A (en) 1988-02-03 1988-02-03 Blends of poly(etheresters) and polyesters
US29837189A 1989-01-18 1989-01-18
US298,371 1989-01-18

Publications (1)

Publication Number Publication Date
WO1989007124A1 true WO1989007124A1 (fr) 1989-08-10

Family

ID=26848911

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1989/000378 WO1989007124A1 (fr) 1988-02-03 1989-01-31 Melanges de poly(etheresters) et de polyesters, et articles ainsi obtenus

Country Status (5)

Country Link
EP (1) EP0397796A1 (fr)
JP (1) JPH04501277A (fr)
AU (1) AU618793B2 (fr)
BR (1) BR8907218A (fr)
WO (1) WO1989007124A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1054038A1 (fr) * 1998-02-06 2000-11-22 Riken Vinyl Industry Co., Ltd. Composition de resine et feuilles en etant faites
WO2005061580A1 (fr) * 2003-12-04 2005-07-07 Eastman Chemical Company Articles faconnes concus a partir de compositions de polyester cycloaliphatique

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2255345A1 (fr) * 1973-12-19 1975-07-18 Du Pont
EP0297423A2 (fr) * 1987-06-30 1989-01-04 Hoechst Celanese Corporation Masse à mouler de polyester ayant des propriétés de traitement modifiées

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2255345A1 (fr) * 1973-12-19 1975-07-18 Du Pont
EP0297423A2 (fr) * 1987-06-30 1989-01-04 Hoechst Celanese Corporation Masse à mouler de polyester ayant des propriétés de traitement modifiées

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1054038A1 (fr) * 1998-02-06 2000-11-22 Riken Vinyl Industry Co., Ltd. Composition de resine et feuilles en etant faites
EP1054038A4 (fr) * 1998-02-06 2002-05-29 Riken Vinyl Ind Composition de resine et feuilles en etant faites
EP1529808A2 (fr) * 1998-02-06 2005-05-11 Riken Technos Corporation Feuille de résine
EP1529809A1 (fr) * 1998-02-06 2005-05-11 Riken Technos Corporation Composition de résine et feuiile à base de résine
EP1529808A3 (fr) * 1998-02-06 2005-05-18 Riken Technos Corporation Feuille de résine
WO2005061580A1 (fr) * 2003-12-04 2005-07-07 Eastman Chemical Company Articles faconnes concus a partir de compositions de polyester cycloaliphatique
US7169880B2 (en) 2003-12-04 2007-01-30 Eastman Chemical Company Shaped articles from cycloaliphatic polyester compositions
US7297755B2 (en) 2003-12-04 2007-11-20 Eastman Chemical Company Shaped articles from cycloaliphatic polyester compositions

Also Published As

Publication number Publication date
BR8907218A (pt) 1991-03-05
JPH04501277A (ja) 1992-03-05
AU3192189A (en) 1989-08-25
EP0397796A1 (fr) 1990-11-22
AU618793B2 (en) 1992-01-09

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