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WO2013030300A1 - Mousses renfermant du carbonate de polypropylène - Google Patents

Mousses renfermant du carbonate de polypropylène Download PDF

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Publication number
WO2013030300A1
WO2013030300A1 PCT/EP2012/066900 EP2012066900W WO2013030300A1 WO 2013030300 A1 WO2013030300 A1 WO 2013030300A1 EP 2012066900 W EP2012066900 W EP 2012066900W WO 2013030300 A1 WO2013030300 A1 WO 2013030300A1
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weight
components
total weight
acid
component
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German (de)
English (en)
Inventor
Andreas Füssl
Jan Kurt Walter Sandler
Sameer Nalawade
Tobias Heinz Steinke
Volker Warzelhan
Andreas KÜNKEL
Klaus Hahn
Jerome LOHMANN
Anna Katharina Brym
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BASF SE
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BASF SE
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    • 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
    • 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
    • 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
    • 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
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Definitions

  • the present invention relates to foam layers based on a biodegradable polyester mixture PM, comprising: i) from 5 to 49% by weight, based on the total weight of components i to ii, of at least one polypropylene carbonate; ii) from 51 to 95% by weight, based on the total weight of components i to ii, of polylactic acid; iii) 0 to 25 wt .-%, based on the total weight of components i to v, of a polyester composed of a (x1) aliphatic and / or (x2) aromatic dicarboxylic acid and a (y) aliphatic diol; iv) 0 to 5 wt .-%, based on the total weight of components i to v, of an epoxy group-containing copolymer based on styrene, acrylic acid ester and / or methacrylic acid ester; and v) 0 to 15% by weight, based on the total weight of components i
  • the present invention further relates to foam layers based on a biodegradable polyester mixture, comprising: i) 5 to 45 wt .-%, based on the total weight of components i and ii, at least one polypropylene carbonate and ii) 55 to 95 wt .-%, based on the total weight of components i to ii, polylactic acid; iii) from 1 to 25% by weight, based on the total weight of components i to v, of a polyester composed of a (x1) aliphatic and / or (x2) aromatic dicarboxylic acid and a (y) aliphatic diol; iv) from 0.05 to 2% by weight, based on the total weight of components i to v, of an epoxide group-containing copolymer based on styrene, acrylate and / or methacrylic acid ester; and v) 0.1 to 5 wt .-%, based on the total weight
  • the present invention relates to a method for producing said foam layers and the use of the foam layers for thermal and acoustic insulation and as packaging material.
  • Polypropylene carbonate itself is difficult to process on an industrial scale to foam (see J. Jiao et al., Journal of Applied Polymer Science, Vol. 102, 2006 5240-47). Very high density foams are obtained (see Comparative Examples 1 and 2).
  • Foam layers of low density in particular less than 200 g / l, more preferably less than 100 g / l, more preferably less than 50 g / l.
  • polyester mixtures containing: i) from 5 to 49% by weight, based on the total weight of components i to ii, of at least one polypropylene carbonate; ii) from 51 to 95% by weight, based on the total weight of components i to ii, of polylactic acid;
  • blowing agents such as in particular carbon dioxide or nitrogen to foam layers with low density.
  • the foam stability could be improved by the use of preferably from 0.05 to 2% by weight, based on the total weight of components i to v, of an epoxide group-containing copolymer based on styrene, acrylic ester and / or methacrylic ester (component iv).
  • a fine-celled foam preferably 0.2 to 3 wt .-%, based on the total weight of components i to v, of a nucleating agent (component v) such as talc or chalk add.
  • polypropylene carbonate (component i) can analogously, for example WO
  • WO2006 / 061237 or WO 2007/125039 are prepared by copolymerization of propylene oxide and carbon dioxide.
  • the polypropylene carbonate chain may contain both ether and carbonate groups.
  • the proportion of carbonate groups in the polymer is dependent on the reaction conditions, in particular the catalyst used.
  • more than 85, and preferably more than 90%, and most preferably more than 95%, of all the linkages are carbonate groups.
  • Suitable zinc and cobalt catalysts are described in US 4789727 and US 7304172.
  • Polypropylene carbonate can also be prepared analogously to Soga et al., Polymer Journal, 1981, 13, 407-10.
  • the polymer is also commercially available and is marketed, for example, by Empower Materials Inc. or Aldrich. More recently, polypropylene carbonates having a polycarbonate content of nearly 100% and a high head-to-tail ratio have been developed by companies such as SK Energy and Novomer (see WO 2010013948, WO2010028362 and WO2010022388). These products are particularly preferred for the foam layers of the invention.
  • the molecular weight Mn of the polypyrene carbonates produced by the abovementioned processes is generally from 70,000 to 90,000 Da.
  • the molecular weight Mw is usually 250,000 to 400,000 Da.
  • Polypropylene carbonates with a Mn of less than 20,000 Da usually have low glass transition temperatures below 20 ° C.
  • the polydispersity ratio of weight average (Mw) to number average (Mn) is usually between 1 and 80 and preferably between 2 and 10. These polypropylene carbonates can be up to 1%
  • Particularly suitable chain extenders for the polypropylene carbonates are MSA, acetic anhydride, di- or polyisocyanates, di- or polyoxazolines or -oxazines or di- or polyepoxides.
  • isocyanates are toluylene-2,4-diisocyanate, toluylene-2,6-diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthylene-1,5-diisocyanate or xylylene diisocyanate and in particular 1,6-hexamethylene diisocyanate, isophorone diisocyanate or methylene bis (4-isocyanatocyclohexane).
  • Particularly preferred aliphatic diisocyanates are isophorone diisocyanate and in particular 1,6-hexam
  • the chain extenders are preferably used in amounts of from 0.01 to 5, preferably from 0.05 to 2, particularly preferably from 0.08 to 1% by weight, based on the amount of polymer.
  • the glass transition temperature Tg drops to as low as 1 ° C.
  • polylactic acid having the following property profile is preferred:
  • melt volume rate (MVR at 190 ° C and 2.16 kg according to ISO 1 133) of 0.5 to 9, preferably 2 to 9 ml / 10 minutes;
  • Tg glass transition point
  • Preferred component ii is, for example, NatureWorks® 4020 or 4043D (polylactide from NatureWorks).
  • polyesters based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compound so-called.
  • component iii partially aromatic polyesters, into consideration.
  • mixtures of several such polyesters are also suitable as component iii.
  • partially aromatic polyesters are also to be understood as meaning polyester derivatives, such as polyether esters, polyester amides or polyetheresteramides.
  • 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 from the documents mentioned above,
  • partially aromatic polyesters include products such as Ecoflex® (BASF SE), Eastar® Bio and Origo-Bi (Novamont).
  • the acid component x of the partially aromatic polyesters contains from 30 to 70, in particular from 40 to 60, mol% of aliphatic dicarboxylic acid x1 and from 30 to 70, in particular from 40 to 60, mol% of aromatic dicarboxylic acid x2.
  • aliphatic acids and the corresponding derivatives x1 are generally those having 2 to 16 carbon atoms, preferably 4 to 6 carbon atoms, into consideration. They can be both linear and branched.
  • the cycloaliphatic dicarboxylic acids which can be used in the context of the present invention are generally those having 7 to 10 carbon atoms and, in particular, those containing 8 carbon atoms. In principle, however, it is also possible to use dicarboxylic acids having a larger number of carbon atoms, for example having up to 30 carbon atoms.
  • Examples which may be mentioned are malonic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid , 1, 3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid, brassylic acid and 2,5-norbornanedicarboxylic acid.
  • the dicarboxylic acids or their ester-forming derivatives may be used singly or as a mixture of two or more thereof.
  • Succinic acid, adipic acid, azelaic acid, sebacic acid and brassylic acid are preferred.
  • aromatic dicarboxylic acid x2 there are generally mentioned those having 8 to 12 carbon atoms, and preferably those having 8 carbon atoms. Examples include terephthalic acid.
  • the diols y are selected from branched or linear alkanediols having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, or cycloalkanediols having 5 to 10 carbon atoms. Particularly preferred are 1, 4-butanediol and 1, 3-propanediol.
  • the polyester component iii may contain other components such as branching or chain extenders.
  • component iii are the following aliphatic-aromatic polyesters: polybutylene adipate terephthalate (PBAT), polybutylene sebacate terephthalate (PBSeT) or polybutylene succinate terephthalate (PBST) and aliphatic polyesters such as polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene succinate adipate (PBSA), Polybutylene succinate sebacate (PBSSe) and polybutylene sebacate (PBSe).
  • PBAT polybutylene adipate terephthalate
  • PBSeT polybutylene sebacate terephthalate
  • PBST polybutylene succinate terephthalate
  • aliphatic polyesters such as polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene succinate adipate (PBSA), Polybutylene succinate sebacate (PBSSe)
  • 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%.
  • biodegradability causes the polyester blends to disintegrate in a reasonable and detectable time.
  • Degradation can be effected enzymatically, hydrolytically, oxidatively and / or by the action of electromagnetic radiation, for example UV radiation, and most of the time, for the most part, be effected by the action of microorganisms such as bacteria, yeasts, fungi and algae.
  • the biodegradability can be quantified, for example, by mixing polyesters with compost and storing them for a certain period of time. For example, according to DIN EN 13432 (referring to ISO 14855), CO 2 -free air is allowed to flow through matured compost during composting and subjected to a defined temperature program.
  • biodegradability is determined by the ratio of the net CO 2 release of the sample (after deduction of CO 2 release by the compost without sample) to the maximum CO 2 release of the sample (calculated from the carbon content of the sample) as a percentage of biodegradation
  • Biodegradable polyesters mixtures generally show signs of decomposition after only a few days of composting, such as fungal growth, cracking and hole formation. Other methods of determining biodegradability are described, for example, in ASTM D 5338 and ASTM D 6400-4.
  • Component iv is an epoxide-group-containing copolymer based on styrene, acrylic ester and / or methacrylic acid ester, which has the following structural features.
  • the epoxy groups bearing units are preferably glycidyl (meth) acrylates. Copolymers having a glycidyl methacrylate content of greater than 20, particularly preferably greater than 30 and especially preferably greater than 50% by weight of the copolymer, have proved to be advantageous.
  • the epoxy equivalent weight (EEW) in these polymers is preferably 150 to 3000, and more preferably 200 to 500 g / equivalent.
  • the weight average molecular weight MW of the polymers is preferably from 2,000 to 25,000, in particular from 3,000 to 8,000.
  • the number average molecular weight Mn of the polymers is preferably 400 to 6,000, especially 1,000 to 4,000.
  • the polydispersity (Q) is generally between 1.5 and 5.
  • Epoxide group-containing copolymers of the abovementioned type are described, for example, by BASF Resins B.V. sold under the trademark Joncryl® ADR. Suitable chain extenders are Jonctyl® ADR 4368 and Cardura® E10 from Shell. Epoxide group-containing copolymers of the abovementioned type are used in 0 to 5% by weight, preferably in 0.05 to 2, and particularly preferably in 0.1 to 1% by weight, based on the components i to v.
  • additives v) are, for example:
  • Nucleating agents such as talc, chalk, carbon black, graphite, calcium or zinc stearate, poly-D-lactic acid, N, N'-ethylene-bis-12-hydroxystearamide, polyglycolic acid,
  • compatibilizers such as silanes, maleic anhydride, fumaric anhydride, isocyanates, diacid chlorides,
  • auxiliaries are used in particular in a concentration of 0 to 15 wt .-%, in particular 0.2 to 3 wt .-% based on the total weight of the components to v.
  • nucleating agents is particularly advantageous and has a positive effect on the production of the foam layers.
  • the finely dispersed nucleating agent represents a surface for cell formation, whereby a homogeneous cell structure can be achieved and the foam density can be influenced.
  • component v) it is preferred to use 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 starch, starch derivatives, cereals, cellulose derivatives, polycaprolactone and polyhydroxyalkanoates, in particular starch, polyhydroxybutyrate (PHB), polyhydroxybutyratecovalenate (PHBV), Biocycle® (polyhydroxybutyrate from PHB Ind .); Enmat® (polyhydroxybutyrate covalenate from Tianan).
  • PHB polyhydroxybutyrate
  • PHBV polyhydroxybutyratecovalenate
  • Biocycle® polyhydroxybutyrate from PHB Ind .
  • Enmat® polyhydroxybutyrate covalenate from Tianan
  • inorganic fillers v the talc, chalk, carbon black and graphite already mentioned as nucleating agents have been found. As a filler, however, they can be used in higher concentrations.
  • the organic and inorganic fillers can be used in a concentration of up to 35% by weight.
  • the biodegradable polyester mixtures in the foam layers according to the invention usually comprise from 5 to 49% by weight, preferably from 5 to 45% by weight, particularly preferably from 10 to 30% by weight of component i and from 51 to 95% by weight. -%, preferably from 55 to 95 wt .-%, particularly preferably from 70 to 90 wt .-% polylactic acid (component ii). From the abovementioned polymer mixtures, foam layers having a very low density of preferably less than 50 g / l and at the same time excellent feel can be obtained (see examples 5 to 7 according to the invention).
  • Another preferred embodiment is based on ternary mixtures of component i (PPC), component ii (polylactic acid) and component iii (aliphatic or partially aromatic polyester).
  • Such polyester mixtures preferably contain from 0 to 25% by weight, preferably from 1 to 25% by weight, and more preferably from 5 to 20% by weight of component iii, wherein the percentages by weight are based on the total weight of components i to v.
  • Component iv is used in 0 to 5 wt .-%, preferably in 0.05 to 2 wt .-%, and particularly preferably in 0.1 to 1 wt .-%, based on the total weight of components i to v.
  • the preparation of the biodegradable polyester mixtures according to the invention from the individual components can be carried out by known processes
  • the method described in WO 2007/0125039 can be used to produce the biodegradable polyester mixtures.
  • the compounding is usually carried out at 150 to 250 ° C - preferably at 180 to 200 ° C - performed.
  • the components are mixed in a single or twin-screw extruder at 160 to 220 ° C. At these temperatures, a homogeneous blend is obtained.
  • blowing agent-laden melt is then cooled in a second extruder. Alternatively, the cooling may be performed in a rear segment of the reflow 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.
  • Foam layers are cooled, for example with air, cut open with a knife and rolled up the resulting smooth foam layers 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 extrusion and winding that the foamed sheets have a homogeneous thickness distribution, since this is of decisive importance for the optionally subsequent thermoforming process.
  • the extruded foam layers can be heated in a thermoforming apparatus by brief and uniform heating, for example with an infrared heating source to 80-120 ° C, more preferably 90-100 ° C and vacuum, optionally with the additional use of compressed air in a tool to a definable thermoformed form of a foam shell and then cooled, for example, with air.
  • a thermoforming apparatus by brief and uniform heating, for example with an infrared heating source to 80-120 ° C, more preferably 90-100 ° C and vacuum, optionally with the additional use of compressed air in a tool to a definable thermoformed form 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 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 optionally iii to v and the mixtures prepared for comparison was determined by pressing these mixtures at 190 ° C. in each case into films having a thickness of 30 ⁇ m. The proportion of undispersed component ii present in these films was assessed by eye examination.
  • 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.
  • Component i (PPC): i-1: The polypropylene carbonate i-1 was prepared analogously to Example 1, WO 2006/061237 (Tg 35 ° C.) and applied in granular form to the heated (100-200 ° C.) opposing roll rolls and heated up.
  • Component iii (PBAT) iii- 1 Ecoflex® FBX 701 1 from BASF SE
  • Component v v-1 Batch containing 90% by weight of components iii-1 and 10% by weight of erucic acid amide
  • Foam production The examples which follow The biodegradable polyester mixtures described were pressed in a brass mold at the indicated temperatures in a hot press with a force of 50 kN to a plate with 1, 5 mm thickness. After cooling, the plate-shaped sample was loaded in a brass dish at the specified constant temperature in a steel pressure vessel (internal volume of 30 ml) for 24 hours with supercritical CO2 at 200 bar pressure. In this case, the samples recorded the saturation concentration of propellant gas achievable with these experimental parameters.
  • a foaming of the homogeneously tempered and saturated with CO2 samples was carried out at the set temperature by a rapid pressure drop; the pressure was released by rapid manual opening of an outlet valve of the autoclave. Immediately after foaming the sample, the autoclave was opened and the sample was taken out.
  • the density of the foamed moldings directly after foaming was determined by the buoyancy method, while the cellular parameters such as the mean cell diameter were determined by evaluation of scanning electron micrographs of at least 2 points on a cross section in the foam produced by cryotraction. For the statistical evaluation, images with at least 10 whole cells in the image section were used.
  • Pure PPC was pressed at 120 ° C to a plate.
  • the temperature for loading and foaming with CO2 in an autoclave was set at 40.degree.
  • Pure PPC was pressed at 120 ° C to a plate.
  • the temperature for loading and foaming with CO2 in the autoclave was set at 50 ° C.
  • the foamed sample shows a minimum density of 287 kg / m 3 .
  • i-1 40% by weight of i-1 (PPC) and 60% by weight of iii-1 were pressed at 170 ° C. into a plate.
  • the temperature for loading and foaming with CO2 in the autoclave was set at 40 ° C.
  • the foamed sample shows a minimum density of 141 kg / m 3 .
  • Comparative Example 4 40% by weight of i-1 and 59% by weight of iii-1 and 1% by weight of v-1 were pressed into a plate at 170 ° C.
  • the temperature for loading and foaming with CO2 in the autoclave was set at 50 ° C.
  • the foamed sample shows a minimum density of 166 kg / m 3 .
  • the melt was fed at a rate of 5 kg / h into a second extruder in order to cool the melt from 200 ° C. to 14 ° C.
  • the propellant loaded melt is conveyed through a hole nozzle with a bore (diameter of the nozzle 1, 7 mm) and a temperature of 145 ° C, the mixture relaxes abruptly and it is obtained a foamed strand.
  • the foamed strand has a minimum density of 44 kg / m 3 .
  • i-1 and ii-1 were melted at a melt temperature of 180 ° C. 8 wt .-% carbon dioxide were mixed into the melt at a melt temperature of 181 ° C.
  • the stated amounts in% by weight relate to the total amount of components i-1 and ii-1.
  • the melt was fed at a rate of 5 kg / h into a second extruder to cool the melt from 200 ° C to 109 ° C.
  • the propellant loaded melt is conveyed through a hole nozzle with a bore (diameter of the nozzle 1, 7 mm) and a temperature of 145 ° C, the mixture relaxes abruptly and it is obtained a foamed strand.
  • the foamed strand has a minimum density of 31 kg / m 3 .
  • i-1 and ii-1 were melted at a melt temperature of 180 ° C.
  • 10 wt .-% carbon dioxide were mixed into the melt at a melt temperature of 180 ° C.
  • the stated amounts in% by weight relate to the total amount of components i-1 and ii-1.
  • the melt was fed at a rate of 5 kg / h into a second extruder to cool the melt from 200 ° C (transition tube) to 1414 ° C.
  • the blowing agent-laden melt is conveyed through a perforated nozzle with a bore (diameter of the nozzle 1, 7 mm) and a temperature of 145 ° C., the mixture expands abruptly and a foamed strand is obtained.
  • the foamed strand has a minimum density of 29 kg / m 3 .

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention concerne des couches de mousse à base d'un mélange de polyester biodégradable PM, renfermant : i) 5 à 49% en poids, par rapport au poids total des constituants i) à ii), d'au moins un carbonate de polypropylène; ii) 51 à 95% en poids, par rapport au poids total des constituants i) à ii), d'acide polylactique; iii) 0 à 25% en poids, par rapport au poids total des constituants i) à v), d'un polyester formé d'un acide dicarboxylique (x1) aliphatique et/ou (x2) aromatique, et d'un (y) diol aliphatique; iv) 0 à 5% en poids, par rapport au poids total des constituants i) à v), d'un copolymère contenant des groupes époxyde, à base de styrène, d'ester d'acide acrylique et/ou d'ester d'acide méthacrylique; et v) 0 à 15% en poids, par rapport au poids total des constituants i) à v) d'additifs.
PCT/EP2012/066900 2011-09-02 2012-08-30 Mousses renfermant du carbonate de polypropylène Ceased WO2013030300A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11179871 2011-09-02
EP11179871.6 2011-09-02

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WO2013030300A1 true WO2013030300A1 (fr) 2013-03-07

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CN114989581A (zh) * 2022-04-24 2022-09-02 宁波能之光新材料科技股份有限公司 一种生物可降解聚乳酸发泡粒子及其制备方法

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