WO1994029378A1 - Melanges de polyester/zeolite - Google Patents

Melanges de polyester/zeolite Download PDF

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Publication number
WO1994029378A1
WO1994029378A1 PCT/US1994/005851 US9405851W WO9429378A1 WO 1994029378 A1 WO1994029378 A1 WO 1994029378A1 US 9405851 W US9405851 W US 9405851W WO 9429378 A1 WO9429378 A1 WO 9429378A1
Authority
WO
WIPO (PCT)
Prior art keywords
zeolite
polyester
ppm
mole percent
group
Prior art date
Application number
PCT/US1994/005851
Other languages
English (en)
Inventor
David Earl Mills
Steven Lee Stafford
Joey Carico Carico
Original Assignee
Eastman Chemical 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
Application filed by Eastman Chemical Company filed Critical Eastman Chemical Company
Priority to BR9406752A priority Critical patent/BR9406752A/pt
Priority to EP94918113A priority patent/EP0702705A1/fr
Publication of WO1994029378A1 publication Critical patent/WO1994029378A1/fr

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/008Additives improving gas barrier properties

Definitions

  • This invention relates to a polyester/zeolite admixture having an excellent gas barrier property and an improved flavor retaining property, and clarity. More particularly, the present invention relates to a polyester/zeolite admixture wherein the zeolite is present in a critical amount of 100 parts per million (ppm) to 1000 ppm.
  • the present inventors have determined that addition of small— or medium— ore zeolites in a critical amount to a polyester reduces the concentration of acetaldehyde in the polyester without producing haze and thus improves the storage property, flavor retaining property, and fragrance retaining property of containers made from such polyester.
  • Polyesters such as polyethylene terephthalate (PET) are widely used for the production of light weight plastic articles since PET is excellent in mechanical properties such as formability and creep resistance and can be biaxially molecularly oriented.
  • PET polyethylene terephthalate
  • acetaldehyde is formed by thermal decomposition of the polyester and when the polyester is formed into an article, the acetaldehyde in the article walls migrates into the contents of the article. Small amounts of acetaldehyde adversely affect the flavor retaining property of foods and beverages, and the fragrance retaining property of foods, beverages, cosmetics, and other package contents. For these reasons, it is desirable to minimize the migration of acetaldehyde into package contents.
  • the use of zeolites in polyesters is disclosed in U.S. Pat. Nos. 3,876,608, 4,391,971 and 5,104,965, and PCT International Publication No. WO 90/03408.
  • U.S. Pat. No. 3,876,608 discloses the addition of 13X or 4A zeolite in polyesters as a inert filler to increase surface roughness of polyester films.
  • the molten polymer film is contacted with a cooling quench drum to obtain amorphous polymer prior to biaxial orientation.
  • Acetaldehyde is not mentioned.
  • U.S. Pat. No. 4,391,971 discloses a method for reducing the acetaldehyde content in PET by passing the PET through a bed of zeolite pellets. In this disclosure, the zeolite is not admixed with the polyester.
  • 5,104,965 discloses a process for preparing a crystalline polyethylene terephthalate which contains greater than 1000 ppm of a zeolite. No mention is made of acetaldehyde or haze. In contrast, the present inventors have determined that a polyester/zeolite admixture wherein the zeolite is present in a critical amount of 100 parts per million (ppm) to 1000 ppm imparts adequate reduction in residual acetaldehyde without imparting haze to the polyester. If smaller than 100 ppm of zeolite is used, an acceptable level of haze can be achieved, however, residual acetaldehyde is very large.
  • PCT International Publication No. WO 90/03408 discloses a process for making oriented PET film containing zeolites as slip additives.
  • the use of zeolites as polymerization catalysts in PET is also disclosed. No mention is made of bottle or sheet applications, only oriented film primarily for magnetic tape applications. Acetaldehyde was not mentioned.
  • polyester/zeolite admixtures which exhibit excellent mechanical properties such as impact resistance, stress crack resistance and heat resistance, and which display excellent melt flowability at the time of molding thereof, and to provide processes for preparing said polyester/zeolite admixture.
  • a polyester/zeolite admixture having improved flavor retaining properties and clarity comprising: (1) a polyester which comprises
  • a dicarboxylic acid selected from the group consisting of aromatic dicarboxylic acids, saturated aliphatic dicarboxylic acids, cycloaliphatic dicarboxylic acids, and combinations thereof, and (b) a diol component comprising repeat units from at least 50 mole percent ethylene glycol, based on 100 mole percent dicarboxylic acid and 100 mole percent diol; and
  • the polyester, component (1) includes copolyesters.
  • the polyester may be crystalline, semi—crystalline or amorphous.
  • the polyester contains repeat units from a dicarboxylic acid and a diol, based on 100 mole percent dicarboxylic acid and 100 mole percent diol.
  • Dicarboxylic acids useful in the present invention include aromatic dicarboxylic acids preferably having 8 to 14 carbon atoms, saturated aliphatic dicarboxylic acids preferably having 4 to 12 carbon atoms, and cycloaliphatic dicarboxylic acids preferably having 8 to 12 carbon atoms.
  • dicarboxylic acids are: terephthalic acid, phthalic acid, isophthalic acid, naphthalene—2,6—dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl—4,4'—dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and the like.
  • the polyester may be prepared from two or more of the above dicarboxylic acids.
  • the diol component contains repeat units from at least 50 mole percent ethylene glycol.
  • diol comonomers which can be included with ethylene glycol are cycloaliphatic diols preferably having 6 to 15 carbon atoms or aliphatic diols preferably having 3 to 8 carbon atoms.
  • diol comonomers are: diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, propane—1,3—diol, butane-1,4-diol, pentane—1,5—diol, hexane-1,6—diol, 3—methylpentanediol-(2,4) , 2—methylpentanediol—(1,4), 2,2,4—trimethylpentane- diol—(1,3), 2—ethylhexanediol-(l,3) , 2,2-diethylpropane- diol—(1,3) , hexanediol-(1,3), 1,4-di-(hydroxyethoxy)- benzene, 2,2—bis—(4—hydroxycyclohexyl)—propane, 2,4— ihydroxy-l,1,3,3—tetramethyl—cyclobutane, 2,2—
  • the polyester may be prepared from one or more of the above diols.
  • the polyester may also contain small amounts of trifunctional or tetrafunctional comonomers such as tri ellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, and other polyester forming polyacids or polyols generally known in the art.
  • the preferred polyester composition contains a dicarboxylic acid component which consists essentially of repeat units from terephthalic acid and a diol component which consists essentially of repeat units from ethylene glycol.
  • Polyesters useful as component (1) have an inherent viscosity of 0.4 to 1.5 dL/g.
  • the polyester has an inherent viscosity of 0.6 to 1.2 dL/g as measured at 25°C. using 0.50 grams of polymer per 100 ml of a solvent consisting of 60% by weight phenol and 40% by weight tetrachloroethane.
  • the polyester may be prepared by conventional polycondensation procedures well—known in the art. Such processes include direct condensation of the dicarboxylic acid(s) with the diol(s) or by ester interchange using a dialkyl dicarboxylate. For example, a dialkyl terephthalate such as dimethyl terephthalate is ester interchanged with the diol(s) at elevated temperatures in the presence of a catalyst.
  • the second component of the present invention is a zeolite.
  • Zeolites are crystalline alumino—silicates with highly ordered crystalline structure. Cavities of a defined size are formed in the rigid, three—dimensional network composed of Si0 4 — and A10 4 -tetrahedra. The lattice contains cavities of varying diameters, depending on the type of zeolite. A distinction is made between large-, medium-, and small—pore zeolites. In the case of large—pore Y—zeolites, for example, a cavity of this type having a diameter of 7.4 angstroms is formed by twelve Si0 4 tetrahedra.
  • zeolites In the case of small—pore A—zeolites, eight tetrahedra form a ring of diameter 4.1 angstroms.
  • the medium—pore pentasil zeolites have a 10—ring system with an ellipsoidal tubular diameter of 5.5 angstroms x
  • All medium—pore zeolites are pentasil zeolites which contain uniform channels.
  • Small—pore and medium—pore zeolites are suitable for use in this invention.
  • Examples of small—pore zeolites include A—zeolites such as 3A, 4A, and 5A, mordenite (small—pore type) such as AW—300 and ZEOLON—300 which are available from Union Carbide and Norton Company, erionite, chabazite, zeolite F such as IONSIV F80, and zeolite W such as IONSIV W85.
  • Examples of medium—pore zeolites include ZSM-5, ZSM-11, ZSM-22, NU-10, Theta 1, ZSM-23, ZSM-48, TS-1, and silicalite.
  • the present inventors have determined that addition of small— or medium—pore zeolites in the range of 100 to 1000 ppm to the polyester, component 1, reduces the concentration of acetaldehyde in the polyester without producing haze and thus improves the storage property, flavor retaining property, and fragrance retaining property of containers made from such polyester.
  • the polyester compositions of this invention are prepared by mixing a polyester with small— or medium—pore zeolites.
  • the zeolites can be readily incorporated into the polyester during the polymerization of the polyester or in a later step by any suitable melt blending process such as batch mixing. single screw, or twin screw extrusion.
  • the zeolite is added during polymerization since this method produces less haze then melt blending. Because zeolites can absorb and release large amounts of water and hence contribute to polymer hydrolysis on melt blending, it is preferable to dehydrate the zeolites by heating to a temperature of greater than 350°C. before adding the zeolites to the polyester melt.
  • thermoformed or injection molded trays examples include, but are not limited to, thermoformed or injection molded cups, extrusion blow molded bottles, injection stretch blow molded bottles, extruded film, and extruded sheet.
  • extrusion blow molded bottles examples include, but are not limited to, thermoformed or injection molded cups, extrusion blow molded bottles, injection stretch blow molded bottles, extruded film, and extruded sheet.
  • Acetaldehyde generation was determined by the following method. After crystallizing for 30 minutes at 180°C. , the pelletized polyester/zeolite admixture was dried overnight at 120°C. in a vacuum oven. A Tinius—Olsen melt indexer was loaded with 5 grams of the polyester or copolyester and held at the test temperature (preferably 275—310°C.) for five minutes. The molten polyester was extruded into water and stored at a temperature of —25°C. until grinding.
  • the sample was ground to 20 mesh or finer and 0.5 grams was placed in a sample tube which was immediately sealed.
  • the sample was analyzed by dynamic headspace gas chromatographic analysis using a Hewlett—Packard 5890 Gas Chromatograph with a Perkin Elmer Automatic Thermal Desorption ATD—50 as the injection system. Acetaldehyde was desorbed by heating the sample at 150°C. for ten minutes.
  • the gas chromatography column had a 30 m by 0.53 mm inside diameter. Haze was determined by ASTM D1003. Haze values of less than 10% are acceptable for high quality packaging.
  • Poly(ethylene terephthalate) was prepared by the following procedure.
  • Bis(2-hydroxyethyl) terephthalate 190.5 grams, was placed in a polymerization reactor along with antimony oxide (225 ppm Sb) , cobalt acetate (65 ppm Co) and ZONYL A (80 ppm phosphorus) .
  • antimony oxide 225 ppm Sb
  • cobalt acetate 65 ppm Co
  • ZONYL A 80 ppm phosphorus
  • the amount and type of zeolite indicated in Table II was also added.
  • the mixture was heated with stirring un-er nitrogen atmosphere to 285 C. and pressure was reduced to 0.3 torr. When the polymer viscosity reached the desired level, the polymerization was terminated by removing the heat source and venting the reactor to ambient pressure.
  • the resulting polyesters had inherent viscosities of 0.57—0.62 dL/g. These polyesters were solid—state polymerized to an inherent viscosity of 0.70-0.72 dL/g.
  • a polyester resin was prepared by mixing powdered 4A zeolite, 0.6 grams, with 599.4 grams of KODAPAK PET 9921W which is available from Eastman Chemical Company, and extruding/pelletizing in a Brabender extruder at 275°C. melt temperature.
  • the zeolite was heated at 500°C. for 12 hours and the PET was dried at 150°C. for 12 hours.
  • the pelletized polyester/zeolite resin was crystallized by heating at 180°C. for 30 minutes and dried in a vacuum oven for 12 hours at 120°C.
  • Acetaldehyde generation was 8.1 ppm at 275°C. and 18.1 ppm at 295°C. compared to 11.0 ppm at 275°C. and 25.5 ppm at 295°C. without the zeolite additive.
  • a polyester resin was prepared by mixing powdered 4A zeolite, 6.0 grams, with 594.0 grams of KODAPAK PET 9921W and extruding/pelletizing in a Brabender extruder at 275°C. melt temperature. The zeolite was heated at 500°C. for 12 hours and the PET was dried at 150°C. for 12 hours. The pelletized polyester/zeolite resin was crystallized by heating at 180°C. for 30 min and dried in a vacuum oven for 12 hours at 120°C. Acetaldehyde generation was 6.7 ppm at 275°C. and 12.7 ppm at 295°C. compared to 11.0 ppm at 275°C. and 25.5 ppm at 295°C. without the zeolite additive.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Cette invention se rapporte à un mélange de polyester/zéolite présentant une excellente propriété de barrière aux gaz ainsi qu'une propriété de conservation de l'arôme améliorée et une bonne transparence. La présente invention se rapporte plus particulièrement à un mélange de polyester/zéolite dans lequel la zéolite est présente dans une quantité critique de 100 parties par million (ppm) à 1000 ppm. Les inventeurs ont déterminé que l'ajout de zéolites aux pores moyens ou petits en quantité critique dans un polyester réduit la concentration de l'acétaldéhyde dans le polyester sans former de voile et améliore ainsi la propriété au stockage, la propriété de conservation de l'arôme et la propriété de conservation du parfum de récipients fabriqués à partir de ce polyester.
PCT/US1994/005851 1993-06-07 1994-05-26 Melanges de polyester/zeolite WO1994029378A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
BR9406752A BR9406752A (pt) 1993-06-07 1994-05-26 Mistura de poliéster/zeólito possuindo aperfeiçoadas propriedades de retençao de aroma e claridade processo para preparar a mesma e artigo plástico moldado pelo calor ou moldado por estiramento
EP94918113A EP0702705A1 (fr) 1993-06-07 1994-05-26 Melanges de polyester/zeolite

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7201593A 1993-06-07 1993-06-07
US08/072,015 1993-06-07

Publications (1)

Publication Number Publication Date
WO1994029378A1 true WO1994029378A1 (fr) 1994-12-22

Family

ID=22105028

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/005851 WO1994029378A1 (fr) 1993-06-07 1994-05-26 Melanges de polyester/zeolite

Country Status (6)

Country Link
EP (1) EP0702705A1 (fr)
BR (1) BR9406752A (fr)
CA (1) CA2163660A1 (fr)
CZ (1) CZ320195A3 (fr)
PL (1) PL311882A1 (fr)
WO (1) WO1994029378A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999032547A1 (fr) * 1997-12-22 1999-07-01 Eastman Chemical Company Procede de production de contenants a partir de compositions constituees de polymere et de particules
EP1149863A1 (fr) * 2000-04-27 2001-10-31 Degussa AG Polymère incolore et à basse émission
WO2004020519A1 (fr) * 2002-08-30 2004-03-11 The Coca-Cola Company Polyester a teneur reduite en acetaldehyde et procede mettant en oeuvre un catalyseur d'hydrogenation
EP1442993A1 (fr) * 2003-01-29 2004-08-04 Eastman Chemical Company Bouchons de bouteilles comprenant des agents absorbant l'acétaldéhyde
WO2005010088A1 (fr) * 2003-07-17 2005-02-03 Colormatrix Corporation Procede permettant de diminuer la teneur en aldehyde des polyesters
US6958405B2 (en) * 2004-03-09 2005-10-25 Arco Chemical Technology, L.P. Polymer-encapsulated titanium zeolites for oxidation reactions
DE102013013163A1 (de) 2013-07-18 2015-01-22 Kautex Textron Gmbh & Co. Kg Mehrlagiges Verbundmaterial und Gegenstände umfassend dasselbe
DE102014010129A1 (de) 2014-07-09 2016-01-14 Kautex Textron Gmbh & Co. Kg Vorratsbehälter zur Aufnahme einer wässrigen Harnstofflösung
EP3047969A1 (fr) 2015-01-22 2016-07-27 Kautex Textron Gmbh&Co. Kg Matériau composite multicouches et objets constitués de celui-ci
CN113214616A (zh) * 2021-06-15 2021-08-06 万华化学(宁波)有限公司 一种应用于食品接触领域的低气味生物可降解pla合金及其制备方法
US12104013B2 (en) * 2017-07-17 2024-10-01 Technip Zimmer Gmbh Method for preparing polyesters

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004054182C5 (de) * 2003-12-12 2015-03-12 Leica Camera Ag Binokulares Fernglas mit integriertem Laser-Entfernungsmesser

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU67676A1 (fr) * 1972-05-26 1973-12-04
US4391971A (en) * 1981-12-28 1983-07-05 The Goodyear Tire & Rubber Company Color improvement and acetaldehyde reduction in high molecular weight polyesters
JPS6270442A (ja) * 1985-09-24 1987-03-31 Diafoil Co Ltd ポリエステル組成物
WO1990003408A1 (fr) * 1988-09-30 1990-04-05 E.I. Du Pont De Nemours And Company Procede ameliore de fabrication de films en terephthalate de polyethylene contenant un lubrifiant
US5104965A (en) * 1991-02-22 1992-04-14 Eastman Kodak Company Process for the preparation of crystalline poly(ethylene terephthalate)
WO1992018554A1 (fr) * 1991-04-18 1992-10-29 Eastman Kodak Company Procede de preparation de copolyesters cristallins
WO1993021264A1 (fr) * 1992-04-14 1993-10-28 Eastman Kodak Company Composition contenant un copolyester et un zeolite

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU67676A1 (fr) * 1972-05-26 1973-12-04
US4391971A (en) * 1981-12-28 1983-07-05 The Goodyear Tire & Rubber Company Color improvement and acetaldehyde reduction in high molecular weight polyesters
JPS6270442A (ja) * 1985-09-24 1987-03-31 Diafoil Co Ltd ポリエステル組成物
WO1990003408A1 (fr) * 1988-09-30 1990-04-05 E.I. Du Pont De Nemours And Company Procede ameliore de fabrication de films en terephthalate de polyethylene contenant un lubrifiant
US5104965A (en) * 1991-02-22 1992-04-14 Eastman Kodak Company Process for the preparation of crystalline poly(ethylene terephthalate)
WO1992018554A1 (fr) * 1991-04-18 1992-10-29 Eastman Kodak Company Procede de preparation de copolyesters cristallins
WO1993021264A1 (fr) * 1992-04-14 1993-10-28 Eastman Kodak Company Composition contenant un copolyester et un zeolite

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 107, no. 6, 10 August 1987, Columbus, Ohio, US; abstract no. 41111 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6337046B1 (en) 1997-12-22 2002-01-08 Eastman Chemical Company Process for producing containers from polymer/platelet particle compositions
WO1999032547A1 (fr) * 1997-12-22 1999-07-01 Eastman Chemical Company Procede de production de contenants a partir de compositions constituees de polymere et de particules
EP1149863A1 (fr) * 2000-04-27 2001-10-31 Degussa AG Polymère incolore et à basse émission
US7041350B1 (en) 2002-08-30 2006-05-09 The Coca-Cola Company Polyester composition and articles with reduced acetaldehyde content and method using hydrogenation catalyst
WO2004020519A1 (fr) * 2002-08-30 2004-03-11 The Coca-Cola Company Polyester a teneur reduite en acetaldehyde et procede mettant en oeuvre un catalyseur d'hydrogenation
EP1442993A1 (fr) * 2003-01-29 2004-08-04 Eastman Chemical Company Bouchons de bouteilles comprenant des agents absorbant l'acétaldéhyde
EP1739026A1 (fr) * 2003-01-29 2007-01-03 Eastman Chemical Company Bouchons de bouteilles comprenant des agents absorbant l'acétaldéhyde
US6911523B2 (en) 2003-07-17 2005-06-28 Colormatrix Corporation Method to decrease the aldehyde content of polyesters
WO2005010088A1 (fr) * 2003-07-17 2005-02-03 Colormatrix Corporation Procede permettant de diminuer la teneur en aldehyde des polyesters
US6958405B2 (en) * 2004-03-09 2005-10-25 Arco Chemical Technology, L.P. Polymer-encapsulated titanium zeolites for oxidation reactions
DE102013013163A1 (de) 2013-07-18 2015-01-22 Kautex Textron Gmbh & Co. Kg Mehrlagiges Verbundmaterial und Gegenstände umfassend dasselbe
US10213995B2 (en) 2013-07-18 2019-02-26 Kautex Textron Gmbh & Co. Kg Multilayered composite material and objects made therefrom
DE102014010129A1 (de) 2014-07-09 2016-01-14 Kautex Textron Gmbh & Co. Kg Vorratsbehälter zur Aufnahme einer wässrigen Harnstofflösung
WO2016005192A1 (fr) 2014-07-09 2016-01-14 Kautex Textron Gmbh & Co. Kg Récipient de stockage pour recevoir une solution aqueuse d'urée
EP3047969A1 (fr) 2015-01-22 2016-07-27 Kautex Textron Gmbh&Co. Kg Matériau composite multicouches et objets constitués de celui-ci
US12104013B2 (en) * 2017-07-17 2024-10-01 Technip Zimmer Gmbh Method for preparing polyesters
CN113214616A (zh) * 2021-06-15 2021-08-06 万华化学(宁波)有限公司 一种应用于食品接触领域的低气味生物可降解pla合金及其制备方法
CN113214616B (zh) * 2021-06-15 2022-07-12 万华化学(宁波)有限公司 一种应用于食品接触领域的低气味生物可降解pla合金及其制备方法

Also Published As

Publication number Publication date
PL311882A1 (en) 1996-03-18
EP0702705A1 (fr) 1996-03-27
CZ320195A3 (en) 1996-05-15
BR9406752A (pt) 1996-02-27
CA2163660A1 (fr) 1994-12-22

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