WO2001000724A1 - Produits extrudes a partir de terephtalate de polyethylene possedant une teneur limitee en acetaldehyde et leur procede de fabrication - Google Patents

Produits extrudes a partir de terephtalate de polyethylene possedant une teneur limitee en acetaldehyde et leur procede de fabrication Download PDF

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Publication number
WO2001000724A1
WO2001000724A1 PCT/US2000/017996 US0017996W WO0100724A1 WO 2001000724 A1 WO2001000724 A1 WO 2001000724A1 US 0017996 W US0017996 W US 0017996W WO 0100724 A1 WO0100724 A1 WO 0100724A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyethylene terephthalate
ppm
extruded products
fact
polyol
Prior art date
Application number
PCT/US2000/017996
Other languages
English (en)
Inventor
Jens-Peter Wiegner
Volkmar Voerckel
Marion Nagel
Rolf Eckert
Marion Sela
Sarat Munjal
Original Assignee
The Dow 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 The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to EP00950271A priority Critical patent/EP1196490A1/fr
Priority to MXPA01013391A priority patent/MXPA01013391A/es
Priority to CA002377237A priority patent/CA2377237A1/fr
Priority to JP2001506731A priority patent/JP2003503573A/ja
Priority to AU63397/00A priority patent/AU6339700A/en
Publication of WO2001000724A1 publication Critical patent/WO2001000724A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids

Definitions

  • the invention relates to extruded products of polyethylene terephthalate with a reduced acetaldehyde content, such as bottles or films, and to a process to produce the same.
  • Polyethylene terephthalate is largely used as a raw material to produce packaging materials, such as bottles.
  • packaging materials such as bottles.
  • polyethylene terephthalate in producing bottles for mineral water requires a very high degree of purity of this polyester.
  • thermal decomposition of the polyethylene terephthalate occurs when this compound is processed into extruded products, breakdown products will be found in the processed polyester in any case.
  • the free acetaldehyde content is of particular importance for the use as a receptacle for mineral water as even ultramicro-traces of this substance would affect the taste of the mineral water.
  • Acetaldehyde forms during the hydrolysis or alcoholysis of vinyl esters of the terephthalic acid that have formed in a purely thermal process, and is also a product of oxidative polyester degradation. Basically, there are three preferred resolutions to this problem.
  • a first option is to stabilize the polyester for high processing temperatures. It is known that phosphor compounds are used as stabilizers (JP 58 047 024, JP 53 026 893, JP 62 199 648, WO 97 44 376, EP 826 713, JP 101 82 805, U.S. Patent 5,874,517), and heterocycles have been described as well (JP 57 049 620).
  • a second option includes the largely complete decomposition of the vinyl esters in the second polycondensation stage, also known as the solid state polymerization (SSP). This is achieved through treatment with water or aliphatic alcohols. Examples of such procedures are found in JP 07 053 698; JP 04 21 1 424; CH 655 938; U.S. Patent 4 591 629; BE 896 505 and JP 56 055 426.
  • SSP solid state polymerization
  • a third option is to "catch" the free acetaldehyde with appropriate chemical compounds.
  • polyamides based on xylylene diamine JP 62 181 336, JP 62 050 328, U.S.
  • Patent 5 258 233 commercial polyamides, such as nylon (EP 714 832, CH 684 537, WO 97 01 427), or special polyamides of terephthalic acid, bis(hydroxymethyl)cyclohexane and bis(aminomethyl)cyclohexane (WO 97 28 218) have been used as "catchers”.
  • acetaldehyde content of the products can be clearly reduced by adding polyols to polyethylene terephthalate prior to, or during extrusion without affecting the processing criteria or product properties. It was further established that specifically polyols with at least one primary hydroxy function and one more primary, secondary or tertiary hydroxy function in the 2 and/or 3 position qualify as acetaldehyde catchers for the specified processing parameters.
  • Relatively low-melting sugar alcohols such as sorbitol, mannitol or xylitol
  • sorbitol mannitol
  • xylitol Relatively low-melting sugar alcohols
  • spraying an aqueous polyol solution onto crystalline polyethylene terephthalate pellets after the second polycondensation stage which is also known as solid state polymerization.
  • a drastic reduction of the molecular weight of the polyester through hydrolysis during processing occurs.
  • the added polyol amount is between 50 ppm and 2,000 ppm, preferably between 200 ppm and 1 ,000 ppm.
  • the concentration of the spray solutions is between 5 percent by weight and 70 percent by weight, preferably between 10 percent by weight and 50 percent by weight.
  • the aqueous polyol solution is sprayed onto the pellets at temperatures between 0°C and 300°C, preferably between 20°C and 220°C.
  • polyethylene terephthalate with a polyol content of up to 25 percent by weight can be made through extrusion, and pelletized.
  • the degradation of the polyester through alcoholysis under the given process conditions in the presence of multivalent alcohols can be reduced to an extent whereby a modified polyester of a viscosity adequate for pelletization is obtained, through a selection of appropriate process conditions, such as retention time and temperature.
  • the retention time is 20 seconds to 450 seconds, preferably between 30 seconds and 150 seconds, with temperatures ranging from 225°C to 300°C, preferably from 230°C to 285°C.
  • the polyester which has been modified through extrusion, can be added to the polyester resin as masterbatch in order to reduce the free acetaldehyde content.
  • ionic compounds are readily soluble ionic compounds, more specifically alkali compounds.
  • An especially favorable processing method is to spray aqueous polyol solutions containing the ionic compounds as additional additives onto crystalline polyethylene terephthalate pellets after the second polycondensation stage.
  • the acetaldehyde generation during the processing of polyethylene terephthalate was measured according to the following method:
  • the polyester was processed on an ES 200-50 injection molding machine by Engel Company, with a screw 30 mm in diameter/and a length-diameter ratio of 20.
  • the components that is dried polyethylene terephthalate and the polyols, were mixed in a stainless steel vessel through intense stirring, and then fed to the material hopper of the injection molding machine, to which a nitrogen curtain was applied. This mixture was processed (melted and homogenized) at temperatures between 270°C and 300°C. This melt was then injected into a cooled mold under pressure processing parameters:
  • the acetaldehyde content of the resins produced as described above was determined according to the following method: At first, the various materials were ground with a 1 mm screen in a centrifugal mill by Retsch Company (ZM 1) in the presence of liquid nitrogen. Approximately 0.1 g to 0.3 g of the ground material was put in a 22 mL sample bottle, and sealed with a polytetrafluoroethylene seal.
  • sample bottles were heated in a temperature-controlled, headspace oven (HS-40 XL headspace autosampler by Perkin Elmer) at 150°C for 90 minutes, and subsequently analyzed through gas chromatography (XL GC AutoSystem by Perkin Elmer) with an external standard.
  • HS-40 XL headspace autosampler by Perkin Elmer XL headspace autosampler by Perkin Elmer
  • gas chromatography XL GC AutoSystem by Perkin Elmer
  • the calibration curve was prepared through complete evaporation of aqueous solutions of different acetaldehyde contents.
  • Tables I and II show the significant reduction of the acetaldehyde content of the modified polyethylene terephthalate as compared to polyesters to which no polyol was added or to which commercial stabilizers were added respectively. It is interesting to note that polyvinyl alcohol with exclusively secondary alcohol functions can generate acetaldehyde through alcoholysis of the vinyl esters, but that it cannot bond the liberated aldehyde.
  • Table II provides an overview of the dependence of the acetaldehyde content on the concentration of added solid polyols.
  • Separating column 2 columns with PL Gel Mixed B, 10 ⁇ m, (300 by 7.5 mm )
  • Table III shows the values for the extruded products of polyethylene terephthalate determined through molecular weight determination.
  • the polyester resin obtained from subsequent processing on the Engel machine had a free acetaldehyde content of 6.5 ppm (approximately 62 percent of the acetaldehyde contained in the reference).
  • Example 3 Similar to embodiment 2), 5 mL of a 10 percent aqueous sorbitol solution were sprayed onto 1 kg of polyethylene terephthalate pellets with a intrinsic viscosity of 0.76 dl_/g at a temperature of 25°C.
  • Table IV shows the acetaldehyde content of the polyester resins as a function of the amount and concentration of the aqueous sugar alcohol solution. The molecular weight of the polyethylene terephthalate after processing is shown in addition. Table IV
  • Table IV illustrates that the acetaldehyde content of polyester resins after processing can be significantly reduced by spraying aqueous polyol solutions on them, specifically sugar alcohol solutions, without considerably reducing their molecular weight, which would affect the properties of the extruded product.
  • Another option to produce products of polyethylene terephthalate with a low acetaldehyde content is through adding a polyol-containing masterbatch to the processed polyester.
  • the polyethylene terephthalate used to produce the sorbitol batch was dried at a temperature of 120°C for 20 hours in a SOMOS drying plant TF 100 (by Mann und Hummel ProTec GmbH) with dry air in a closed circuit.
  • the sorbitol batch was produced on the ZSK 30, a two-shaft laboratory kneading extruder with co-rotating anticlockwise screws, made by Werner und Pfleiderer Company.
  • the screw diameter is 30.7 mm and the screw length is 1 ,241 mm, which equals 40.4 D.
  • the plasticizing, mixing and dispersing process occurs via 3 kneading element blocks in the compression and metering zones.
  • the metering zone is provided with a vacuum degassing opening.
  • the product was discharged via orifice nozzles.
  • the d-sorbitol was fed together with the polyethylene terephthalate pellets via feeder 1 to which a permanent nitrogen curtain is applied, or into the compression zone via sidefeeder 2. Precise metering of the individual components was achieved through the use of electronic differential metering balances. Adding more than 20 percent of sorbitol via the sidefeeder was not feasible as the polyethylene terephthalate melt could not absorb the (liquid) sorbitol which had molten at the hot funnel wall to a large extent.
  • the polyethylene terephthalate was dried in a circulated-air drying oven by Binder Company, to which a nitrogen curtain was applied. Drying temperature: 160°C
  • the sorbitol batch was made on the DSK 42/6 by Brabender Company, an internal counter-rotating twin-screw compounder.
  • the screw diameter was 43 mm, and the process length 6D. Forced conveying and a narrow retention time range are provided by the sense of rotation of the machine. D-sorbitol was added together with the polyethylene terephthalate via the nitrogen-purged screw metering unit with speed control.
  • the polyethylene terephthalate was dried in a circulated-air drying oven by Binder Company, to which a nitrogen curtain was applied.
  • sorbitol was simulated by means of the W50 EHT measuring kneader by Brabender Company. Measuring kneaders are used to test processes, such as mixing, compounding or plasticizing of polymers, chemicals or additives, under production-geared conditions.
  • the dried polyethylene terephthalate was fed to the kneading chamber together with the d-sorbitol, and a nitrogen curtain was applied during kneading.
  • Kneading chamber volume 55 cm 3 Kneading machine temperature: 240°C Mass temperature: 247°C Kneading blade speed: 60 rpm
  • Table VI shows the results gained from acetaldehyde generation achieved through the addition of a polyethylene terephthalate /sorbitol batch during polyester processing.
  • Table VI Use of Sorbitol-Containing Polyethylene Terephthalate as a Masterbatch to Reduce the Acetaldeh de Generation Durin ol ester Processin .
  • Table VII shows the results for the reduction of the acetaldehyde content through spraying polyol solutions, to which additionally ionic compounds were admixed, onto the polyester at room temperature.
  • Table VII illustrates the effect of ionic compounds in the range from 1 ppm to 50 ppm.
  • the polyethylene terephthalate is treated with aqueous polyol solutions at higher temperatures, the polyols will be less efficient in reducing the acetaldehyde content of the extruded products, and the processed polyesters will be slightly colored. Adding ionic compounds will increase the efficiency of the polyols and reduce the slight coloring of the processed polyesters.
  • Table VIII summarizes these results and illustrates the surprising effect of ionic admixtures with regard to the color of the processed polyesters and the efficiency of the polyols as aldehyde catchers.
  • the addition of polyols constitutes a simple method of significantly reducing the acetaldehyde content of extruded products made of polyethylene terephthalate resins.
  • ionic compounds in the range from 0.1 ppm to 100 ppm further increases the efficiency of the polyols as aldehyde catchers and that the slight colorings can be reduced by spraying aqueous solutions of these additives on the polyethylene terephthalate pellets at higher temperatures.
  • the subject process to reduce the acetaldehyde content in extruded products of polyethylene terephthalate can be used alone, or together with other methods to reduce the acetaldehyde content, such as the inclusion of comonomers to reduce the processing temperatures, the use of special catalysts, or the deactivation of catalysts.
  • combinations of different acetaldehyde catchers, such as polyol/polyamide, can be used to reduce the acetaldehyde content in extruded products made of polyethylene terephthalate.

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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)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

On utilise des polyols possédant au moins une fonction hydroxy primaire et au moins une autre fonction hydroxy primaire, secondaire ou tertiaire en position 2 et/ou 3, en tant qu'additifs en concentrations de 50 ppm à 5.000 ppm, de façon à limiter la teneur en acétaldéhyde de produits extrudés de téréphtalate de polyéthylène. On utilise, de préférence, des alcools de sucre, tels que sorbitol, mannitol ou xylitol. On peut, de plus, mélanger des composés ioniques, de préférence, des composés ioniques facilement solubles, tels que des composés d'alcalis, en quantité de 0,05 ppm à 50 ppm. D'après l'invention, on pulvérise des solutions aqueuses de polyol sur des granules de téréphtalate de polyéthylène après polycondensation ou après la deuxième étape de polycondensation, connue également sous la désignation de polymérisation à l'état solide, ou on produit lesdites granules par extrusion avec une teneur en polyol inférieure ou égale à 25 % en poids, on obtient les granules après l'opération d'extrusion et on les mélange sous forme de mélange maître avec un polyester préalablement au traitement.
PCT/US2000/017996 1999-06-30 2000-06-29 Produits extrudes a partir de terephtalate de polyethylene possedant une teneur limitee en acetaldehyde et leur procede de fabrication WO2001000724A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP00950271A EP1196490A1 (fr) 1999-06-30 2000-06-29 Produits extrudes a partir de terephtalate de polyethylene possedant une teneur limitee en acetaldehyde et leur procede de fabrication
MXPA01013391A MXPA01013391A (es) 1999-06-30 2000-06-29 Productos extruidos a partir de tereftalato de polietileno con un contenido reducido de acetaldehido, y proceso para su produccion.
CA002377237A CA2377237A1 (fr) 1999-06-30 2000-06-29 Produits extrudes a partir de terephtalate de polyethylene possedant une teneur limitee en acetaldehyde et leur procede de fabrication
JP2001506731A JP2003503573A (ja) 1999-06-30 2000-06-29 低減されたアセトアルデヒド含有分を有するポリエチレンテレフタレートの押出製品及びその製造方法
AU63397/00A AU6339700A (en) 1999-06-30 2000-06-29 Extruded products from polyethylene terephthalate with reduced acetaldehyde content and process of their production

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US14174399P 1999-06-30 1999-06-30
US60/141,743 1999-06-30
US14995499P 1999-08-19 1999-08-19
US60/149,954 1999-08-19
US17668500P 2000-01-18 2000-01-18
US60/176,685 2000-01-18
US20485900P 2000-05-17 2000-05-17
US60/204,859 2000-05-17

Publications (1)

Publication Number Publication Date
WO2001000724A1 true WO2001000724A1 (fr) 2001-01-04

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PCT/US2000/017996 WO2001000724A1 (fr) 1999-06-30 2000-06-29 Produits extrudes a partir de terephtalate de polyethylene possedant une teneur limitee en acetaldehyde et leur procede de fabrication

Country Status (7)

Country Link
EP (1) EP1196490A1 (fr)
JP (1) JP2003503573A (fr)
AR (1) AR024614A1 (fr)
AU (1) AU6339700A (fr)
CA (1) CA2377237A1 (fr)
MX (1) MXPA01013391A (fr)
WO (1) WO2001000724A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002053643A1 (fr) * 2000-12-29 2002-07-11 Ciba Specialty Chemicals Holding Inc. Compositions de polyester a faible teneur residuelle en aldehyde
WO2002079310A2 (fr) * 2001-03-28 2002-10-10 Ciba Specialty Chemicals Holding Inc. Procede de preparation d'un polyester stabilise
WO2003016401A1 (fr) * 2001-08-13 2003-02-27 Ciba Specialty Chemicals Holding Inc. Compositions de polyester a faible contenu en aldehyde residuel
WO2004106424A1 (fr) * 2003-05-27 2004-12-09 The Coca-Cola Company Procede pour reduire la teneur en acetaldehyde de polyesters traites par fusion
US6878457B2 (en) 2002-06-05 2005-04-12 Cellresin Technologies, Llc Reducing concentration of organic materials with substituted cyclodextrin compound in polyester packaging materials
US6908650B2 (en) 2001-03-02 2005-06-21 Ciba Specialty Chemicals Corporation Polyester and polyamide compositions of low residual aldehyde content
US6924132B1 (en) 1995-12-28 2005-08-02 Kyowa Hakko Kogyo Co., Ltd. Protein complementing yeast low temperature-sensitivity fermentability
WO2013174789A1 (fr) 2012-05-23 2013-11-28 Nestec S.A. Dispositif d'identification du contenu d'une capsule pour boisson
WO2019098979A3 (fr) * 2017-11-17 2019-06-13 Erciyes Universitesi Procédé d'inhibition de produits chimiques nocifs formés dans des matériaux fabriqués et semi-fabriqués produits à partir de pet
CN111073234A (zh) * 2019-12-30 2020-04-28 浙江新力新材料股份有限公司 耐热阻燃pet复合材料及其制备方法和在制备插线板中的应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9909956D0 (en) * 1999-04-29 1999-06-30 Univ Aston Thermoplastic moulding compositions and polymer additives

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4394470A (en) * 1981-03-20 1983-07-19 Akzo N.V. Colored polyethylene terephthalate moulding compound and moulded products made therefrom
US4873279A (en) * 1986-12-22 1989-10-10 General Electric Company Copolyester-carbonate and polyester resin blends exhibiting improved color properties
EP0590647A1 (fr) * 1992-09-30 1994-04-06 Union Carbide Chemicals & Plastics Technology Corporation Pulvérisation d'additifs pour plastique sur des polymères
DE4239260A1 (de) * 1992-11-21 1994-05-26 Zimmer Ag Verfahren zur Herstellung von feinteilige Additive enthaltendem Polyester-Masterbatch
EP0691370A2 (fr) * 1994-07-07 1996-01-10 Mitsubishi Chemical Corporation Composition de résine polyester ignifugée

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4394470A (en) * 1981-03-20 1983-07-19 Akzo N.V. Colored polyethylene terephthalate moulding compound and moulded products made therefrom
US4873279A (en) * 1986-12-22 1989-10-10 General Electric Company Copolyester-carbonate and polyester resin blends exhibiting improved color properties
EP0590647A1 (fr) * 1992-09-30 1994-04-06 Union Carbide Chemicals & Plastics Technology Corporation Pulvérisation d'additifs pour plastique sur des polymères
DE4239260A1 (de) * 1992-11-21 1994-05-26 Zimmer Ag Verfahren zur Herstellung von feinteilige Additive enthaltendem Polyester-Masterbatch
EP0691370A2 (fr) * 1994-07-07 1996-01-10 Mitsubishi Chemical Corporation Composition de résine polyester ignifugée

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6924132B1 (en) 1995-12-28 2005-08-02 Kyowa Hakko Kogyo Co., Ltd. Protein complementing yeast low temperature-sensitivity fermentability
US6790499B2 (en) 2000-12-29 2004-09-14 Ciba Speicalty Chemicals Corporation Polyester compositions of low residual aldehyde content
WO2002053643A1 (fr) * 2000-12-29 2002-07-11 Ciba Specialty Chemicals Holding Inc. Compositions de polyester a faible teneur residuelle en aldehyde
US7022390B2 (en) 2001-03-02 2006-04-04 Ciba Specialty Chemicals Corporation Polyester and polyamide compositions of low residual aldehyde content
US6908650B2 (en) 2001-03-02 2005-06-21 Ciba Specialty Chemicals Corporation Polyester and polyamide compositions of low residual aldehyde content
WO2002079310A2 (fr) * 2001-03-28 2002-10-10 Ciba Specialty Chemicals Holding Inc. Procede de preparation d'un polyester stabilise
WO2002079310A3 (fr) * 2001-03-28 2002-12-19 Ciba Sc Holding Ag Procede de preparation d'un polyester stabilise
JP2004523637A (ja) * 2001-03-28 2004-08-05 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド 安定化されたポリエステルの調製方法
US7514526B2 (en) 2001-03-28 2009-04-07 Ciba Specialty Chemicals Corp. Process for preparing a stabilized polyester
US7205379B2 (en) 2001-03-28 2007-04-17 Ciba Specialty Chemicals Corp. Process for preparing a stabilized polyester
WO2003016401A1 (fr) * 2001-08-13 2003-02-27 Ciba Specialty Chemicals Holding Inc. Compositions de polyester a faible contenu en aldehyde residuel
US6974603B2 (en) 2002-06-05 2005-12-13 Cellresin Technologies, Llc Reducing concentration of organic materials with substituted cyclodextrin compound in polyester packaging materials
US7018712B2 (en) 2002-06-05 2006-03-28 Cellresin Technologies, Llc Reducing concentration of organic materials with substituted cyclodextrin compound in polyester packaging materials
US6878457B2 (en) 2002-06-05 2005-04-12 Cellresin Technologies, Llc Reducing concentration of organic materials with substituted cyclodextrin compound in polyester packaging materials
CN100404598C (zh) * 2003-05-27 2008-07-23 可口可乐公司 降低熔融加工的聚酯中乙醛含量的方法
EA010584B1 (ru) * 2003-05-27 2008-10-30 Дзе Кока-Кола Компани Способ снижения содержания ацетальдегида в формованных из расплава полиэфирах, изделие из полиэфира, способ его изготовления и композиция для его изготовления
WO2004106424A1 (fr) * 2003-05-27 2004-12-09 The Coca-Cola Company Procede pour reduire la teneur en acetaldehyde de polyesters traites par fusion
WO2013174789A1 (fr) 2012-05-23 2013-11-28 Nestec S.A. Dispositif d'identification du contenu d'une capsule pour boisson
WO2019098979A3 (fr) * 2017-11-17 2019-06-13 Erciyes Universitesi Procédé d'inhibition de produits chimiques nocifs formés dans des matériaux fabriqués et semi-fabriqués produits à partir de pet
CN111073234A (zh) * 2019-12-30 2020-04-28 浙江新力新材料股份有限公司 耐热阻燃pet复合材料及其制备方法和在制备插线板中的应用
CN111073234B (zh) * 2019-12-30 2022-04-08 浙江新力新材料股份有限公司 耐热阻燃pet复合材料及其制备方法和在制备插线板中的应用

Also Published As

Publication number Publication date
AR024614A1 (es) 2002-10-16
EP1196490A1 (fr) 2002-04-17
MXPA01013391A (es) 2002-07-02
JP2003503573A (ja) 2003-01-28
CA2377237A1 (fr) 2001-01-04
AU6339700A (en) 2001-01-31

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