EP2121839A1 - Couche de mousse à alvéoles fermées à base d'acide polylactique - Google Patents

Couche de mousse à alvéoles fermées à base d'acide polylactique

Info

Publication number
EP2121839A1
EP2121839A1 EP08716789A EP08716789A EP2121839A1 EP 2121839 A1 EP2121839 A1 EP 2121839A1 EP 08716789 A EP08716789 A EP 08716789A EP 08716789 A EP08716789 A EP 08716789A EP 2121839 A1 EP2121839 A1 EP 2121839A1
Authority
EP
European Patent Office
Prior art keywords
weight
components
foam layer
foam
total weight
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.)
Withdrawn
Application number
EP08716789A
Other languages
German (de)
English (en)
Inventor
Björn DIETRICH
Daniela Longo
Gabriel Skupin
Florian KRÜCKL
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP08716789A priority Critical patent/EP2121839A1/fr
Publication of EP2121839A1 publication Critical patent/EP2121839A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • 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
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function

Definitions

  • the present invention relates to foam layers based on a biodegradable polyester blend comprising
  • iii) from 0.5 to 3% by weight, based on the total weight of components i to ii, of a nucleating agent
  • v) 0 to 50% by weight of inorganic or organic filler, wherein the foam layer is in a proportion of greater than 70% of closed cells and has a density of less than 35 g / l.
  • the present invention relates to processes for the preparation of said foam layers and the use of the foam layers for the production of moldings, films and moldings, films containing said foam layers.
  • JP 2004-067894 describes polyester blends based on polylactide and biodegradable aliphatic / aromatic polyesters. Although the authors mention that the polyester blends foam, no foam layers are produced. Also, nothing is done about the chemical and physical properties of the foams.
  • JP 2005-179537 discloses high polylactide polyester blends and aliphatic / aromatic polyethyleneterephthalate based polyesters which are slow to biodegrade.
  • the foams have a density of 40 to 200 g / l. Foam layers are not described.
  • foam films based on biodegradable, aliphatic / aromatic polyesters and cellulose acetate are produced by means of direct direct gasification with carbon dioxide.
  • the films have a high density of greater than 200 to 600 g / l.
  • foam layers of low density in particular less than 40 g / l. It would also be desirable to provide high density (greater than 70%) closed cell foam sheets since these have better thermal insulating properties than open celled foams.
  • foams of biodegradable polymers preferably of renewable raw materials, which can be produced without blowing agents such as hydrocarbon or fluorinated hydrocarbons.
  • inert propellants such as nitrogen and, in particular, carbon dioxide, has the environmental advantage of allowing the foam layers thus produced to be used in the food sector.
  • the present invention is therefore based on the object to provide foam layers of biodegradable materials that do not have the above-mentioned disadvantages.
  • polyester mixtures comprising i) 30 to 10 wt .-%, based on the total weight of components i to ii, of at least one polyester based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compound;
  • ii) from 70 to 90% by weight, based on the total weight of components i to ii, of polylactide (PLA);
  • iii 0.5 to 3% by weight, based on the total weight of components i to ii, of a nucleating agent
  • additives such as lubricants and antiblocking agents, waxes, antistatic agents, antifoggants
  • inorganic or organic fillers such as polymers of renewable raw materials, for example starch, cellulose, cereals, polyhydroxyalkanoates or polycaprolactone or aliphatic polyesters,
  • blowing agents such as carbon dioxide or nitrogen
  • foam layers with low density and high proportion of closed cells.
  • blowing agents such as carbon dioxide or nitrogen
  • the low densities are made possible on the one hand by the special composition of the polyester mixtures according to the invention and by the homogeneous mixing in a twin-screw extruder.
  • Suitable partially aromatic polyesters include linear non-chain extended polyesters (WO 92/09654). Preferred are chain-extended and / or branched partially aromatic polyesters. The latter are known from the documents cited at the outset, WO 96/15173 to 15176, 21689 to 21692, 25446, 25448 or WO 98/12242, to which reference is expressly made. Mixtures of different partially aromatic polyesters are also possible. In particular, partially aromatic polyesters are products such as Ecoflex® (BASF Aktiengesellschaft), Eastar® Bio and Origo-Bi® (Novamont).
  • the abovementioned partially aromatic polyesters and the polyester mixtures according to the invention are generally biodegradable.
  • the characteristic "biodegradable" for a substance or a mixture of substances is fulfilled if this substance or the mixture of substances in at least one of the three methods defined in DIN V 54900-2 (pre-standard, September 1998) a percentage degree of biodegradation of at least 60%.
  • Other methods of determining biodegradability are described, for example, in ASTM D 5338 and ASTM D 6400.
  • the preferred partially aromatic polyesters are characterized by a molecular weight (Mn) in the range from 1000 to 100,000, in particular in the range from 9,000 to 75,000 g / mol, preferably in the range from 10,000 to 50,000 g / mol and a melting point in the range from 60 to 170, preferably in the range of 80 to 150 0 C.
  • Mn molecular weight
  • melt volume rate (MVR at 190 0 C and 2.16 kg according to ISO 1133 of 0.5 - preferably 2 - to 9 ml / 10 minutes
  • Preferred component ii is, for example, NatureWorks® 4020 or 4042D (polylactide from NatureWorks).
  • Component iii is to be understood as meaning a nucleating agent such as talc, chalk, carbon black, graphite, calcium or zinc stearate, poly-D-lactic acid, N, N'-ethylene-bis-12-hydroxystearamide, polyglycolic acid.
  • talc and chalk are preferred.
  • Particularly advantageous for a high cell count of the foam, the use of talc or chalk has proven with a particle size of less than 6 microns.
  • the addition of nucleating agents has a positive effect on the production of the foam layers.
  • the finely dispersed nucleating agent constitutes a surface for cell formation, whereby a homogeneous cell structure can be achieved and the foam density can be influenced.
  • additives iv) are, for example, lubricants and antiblocking agents,
  • auxiliaries are used in particular in a concentration of 0.1 to 10% by weight and preferably of 0.1 to 2% by weight, based on the total weight of components i) and ii).
  • component iv) epoxide-group-containing or unsubstituted natural oils, fatty acid esters or fatty acid amides such as erucamide or Merginat® ESBO.
  • Polymers of renewable raw materials such as, for example, starch, starch derivatives, cereals, cellulose derivatives, polycaprolactone and polyhydroxyalkanoates, and in particular starch, polyhydroxybutyrate (PHB), polyhydroxybutyratecovalerate (PHBV) .
  • PHB polyhydroxybutyrate
  • PHBV polyhydroxybutyratecovalerate
  • Biocycle® polyhydroxybutyrate from Fa. PHB Ind.
  • Enmat® polyhydroxybutyrate covalerate from Tianan
  • inorganic fillers the already mentioned as nucleating agent talc, chalk, carbon black and graphite have been found. As a filler, however, they can be used in higher concentrations.
  • the biodegradable polyester mixtures according to the invention comprise from 10 to 30% by weight, preferably from 15 to 25% by weight of component i and from 70 to 90% by weight, preferably from 75 to 85% by weight of component ii, where the weight percentages in each case based on the total weight of the components i to ii and together give 100 wt .-%.
  • Component iii) is used in 0.5 to 3% by weight and preferably in 1 to 2% by weight, based on the total weight of components i) to ii).
  • biodegradable polyester mixtures according to the invention from the individual components can be carried out by known processes (EP 792 309 and US Pat. No. 5,883,199).
  • all components i, ii and iii can be mixed and reacted in a process step in mixing devices known to the person skilled in the art, for example kneaders or extruders at elevated temperatures, for example from 120 ° C. to 250 ° C.
  • the reaction is preferably carried out in the presence of a radical initiator.
  • the components are mixed in a twin-screw extruder at 160 to 220 ° C. At these temperatures will be a homogeneous blend obtained.
  • PLA component ii
  • blowing agent In the melt is added 1-25 wt .-%, preferably 1-15 wt .-% blowing agent.
  • Physical blowing agents are used to ensure a low foam density.
  • suitable blowing agents are linear alkanes having preferably 4-6 carbon atoms, nitrogen, carbon dioxide, ethanol, dimethyl ether, diethyl ether, methyl ethyl ether and combinations thereof. Particularly preferred are butane, pentane, nitrogen, and carbon dioxide, in particular carbon dioxide.
  • the melt is then cooled in a second twin-screw extruder. Alternatively, the cooling may be performed in a rear segment of the single screw melt extruder. At the selected temperatures, it must be ensured that the pressure in the extruder is sufficiently high to prevent potential premature foaming in the extruder. If a hole nozzle is used to obtain foam strands, which have a smooth, shiny surface.
  • annular nozzle geometry may be used to obtain tubular foam layers.
  • the extruded tubular foam layers are cooled, for example with air, cut open with a knife and the resulting smooth foam layers rolled up on a roller. Care should be taken to unroll at a constant speed. The unwinding speed can influence the foam density. In addition, it must be ensured during the extrusion and winding that the foamed sheets have a homogeneous thickness distribution, since this is of crucial importance for the subsequent thermoforming process.
  • the extruded foam layers can be heated to a thermoforming apparatus by brief and uniform heating, for example with an infrared heating source at 80-120 0 C, more preferably 90-100 0 C and vacuum, optionally with the additional use of compressed air in a tool thermoformed a defined shape of a foam shell and then cooled, for example, with air.
  • a particular field of application of the biodegradable polyester blends with reduced oil and water absorption relates to the use for the production of foam layers, for the presentation of foamed packaging, such as thermoformed food packaging.
  • the molecular weight M n of the partially aromatic polyesters was determined as follows:
  • HFIP hexafluoroisopropanol
  • the melting temperatures of the semiaromatic polyesters were determined by DSC measurements with a device Exstet DSC 6200R from Seiko:
  • the homogeneity of the mixtures of components i, ii, and iii and of the mixtures prepared for the comparison was determined by pressing these mixtures at 190 ° C. in each case into films having a thickness of 30 .mu.m. The proportion of non-dispersed component ii present in these films was assessed by visual inspection.
  • foam layers having a thickness of 2 to 3 mm were prepared by extrusion and use of an annular die. The density was determined by weighing the foam sample and determining the displacement volume in water.
  • Cell wall thickness and morphology were determined by transmission electron microscopy and scanning electron microscopy.
  • polyester i-1 To prepare polyester i-1, 87.3 kg of dimethyl terephthalate, 80.3 kg of adipic acid, 17 grams of 1, 4-butanediol and 0.2 kg of glycerol were mixed together with 0.028 kg of tetrabutyl orthotitanate (TBOT) Molar ratio between alcohol components and acid component 1, 30 was. The reaction mixture was heated to a temperature of 180 ° C. and reacted at this temperature for 6 hours. Subsequently, the temperature was raised to 240 0 C and distilling off the excess dihydroxy compound under vacuum over a period of 3h. 0.9 kg of hexamethylene diisocyanate were then in- ner endeavour 1 h slowly metered in at 240 0 C.
  • TBOT tetrabutyl orthotitanate
  • the resulting polyester i-1 had a melting temperature of 119 ° C. and a molecular weight (M n ) of 23,000 g / mol (corresponds to Ecoflex® FBX 701 1, manufactured by BASF Aktiengesellschaft).
  • ii-1 aliphatic polyester, polylactide Natureworks® 4042D from NatureWorks.
  • the foams of Examples 1 to 3 all show an extremely low density and a high content of closed cells.
  • the foam layers according to the invention have an excellent resilience and a very good thermal insulation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des couches de mousse à base d'un mélange de polyesters biodégradables, comprenant i) 30 à 10% en poids, relativement au poids total des composants i à ii, d'au moins un polyester à base d'acides dicarboxyliques aliphatiques et aromatiques et de diols aliphatiques, contenant ii) 70 à 90 % en poids, relativement au poids total des composants i à ii, de polylactide, et iii) 0,5 à 3 % en poids, relativement au poids total des composants i à ii, d'un agent de nucléation, iv) 0 à 10 % en poids d'additifs; et v) 0 à 50 % en poids de charge anorganique ou organique. La couche de mousse est composée à plus de 70% de cellules fermées et présente une densité inférieure à 35 g/l. L'invention porte également sur des procédés de fabrication des couches de mousse susmentionnées, sur l'utilisation de ces couches de mousse pour fabriquer des pièces moulées et des feuilles, et sur des pièces moulées et des feuilles contenant lesdites couches de mousse.
EP08716789A 2007-02-15 2008-02-11 Couche de mousse à alvéoles fermées à base d'acide polylactique Withdrawn EP2121839A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08716789A EP2121839A1 (fr) 2007-02-15 2008-02-11 Couche de mousse à alvéoles fermées à base d'acide polylactique

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07102497 2007-02-15
EP08716789A EP2121839A1 (fr) 2007-02-15 2008-02-11 Couche de mousse à alvéoles fermées à base d'acide polylactique
PCT/EP2008/051592 WO2008098889A1 (fr) 2007-02-15 2008-02-11 Couche de mousse à alvéoles fermées à base d'acide polylactique

Publications (1)

Publication Number Publication Date
EP2121839A1 true EP2121839A1 (fr) 2009-11-25

Family

ID=39493520

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08716789A Withdrawn EP2121839A1 (fr) 2007-02-15 2008-02-11 Couche de mousse à alvéoles fermées à base d'acide polylactique

Country Status (2)

Country Link
EP (1) EP2121839A1 (fr)
WO (1) WO2008098889A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8455560B2 (en) 2007-02-15 2013-06-04 Basf Se Foam layer produced of a biodegradable polyester mixture
EP2370508A1 (fr) * 2008-12-02 2011-10-05 Metalbolix Inc. Fabrication de mousse de polyhydroxyalcanoate
WO2011086030A2 (fr) * 2010-01-14 2011-07-21 Basf Se Procédé de préparation de granulats expansibles contenant de l'acide polylactique
US9475930B2 (en) 2012-08-17 2016-10-25 Metabolix, Inc. Biobased rubber modifiers for polymer blends
EP2759569B1 (fr) * 2013-01-24 2019-10-16 So.F.Ter. Tecnopolimeri Srl Composition à base d'acide polylactique, procédé de traitement d'une composition à base d'acide polylactique dans un article moulé
EP3004225A1 (fr) 2013-05-30 2016-04-13 Metabolix, Inc. Mélanges de recyclat
CN105452375B (zh) * 2013-08-05 2017-07-21 诺瓦蒙特股份公司 用于制造具有高热变形温度的制品的可生物降解聚合物组合物
CN106459544B (zh) 2014-03-27 2021-10-01 Cj 第一制糖株式会社 高度填充的聚合物体系
CN109251488B (zh) * 2018-09-20 2021-02-05 中国科学院长春应用化学研究所 一种可生物降解的转光膜及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4223245B2 (ja) * 2002-08-07 2009-02-12 ユニチカ株式会社 生分解性ポリエステル樹脂組成物、その製造方法、及びそれより得られる発泡体、成形体
JP2005179537A (ja) * 2003-12-19 2005-07-07 Rai Wen-Jen ポリラクチドの発泡方法及びその発泡体

Non-Patent Citations (1)

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Title
See references of WO2008098889A1 *

Also Published As

Publication number Publication date
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