WO2012113744A1 - Feuille de polyester contenant des sels nutritifs - Google Patents

Feuille de polyester contenant des sels nutritifs Download PDF

Info

Publication number
WO2012113744A1
WO2012113744A1 PCT/EP2012/052841 EP2012052841W WO2012113744A1 WO 2012113744 A1 WO2012113744 A1 WO 2012113744A1 EP 2012052841 W EP2012052841 W EP 2012052841W WO 2012113744 A1 WO2012113744 A1 WO 2012113744A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyester film
aliphatic
biodegradable
polyester
film according
Prior art date
Application number
PCT/EP2012/052841
Other languages
German (de)
English (en)
Inventor
Kai Oliver Siegenthaler
Gregory Von Abendroth
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
Publication of WO2012113744A1 publication Critical patent/WO2012113744A1/fr

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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08K3/012—Additives activating the degradation of the macromolecular compounds
    • 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
    • C08K3/10—Metal compounds

Definitions

  • the present invention relates to a biodegradable polyester film comprising:
  • a polyester of aliphatic and / or aromatic dicarboxylic acids at least one of the dicarboxylic acids being an aliphatic C 1 to C 20 dicarboxylic acid, and aliphatic diols or a biodegradable polymer mixture containing such a polyester and ii) from 0.01 to 1.50% by weight of a nutrient salt mixture comprising: a) at least one nitrogen-containing cation or anion,
  • polyester films at least one cation selected from the group consisting of: K + , Na + , Ca 2+ , Mg : and Fe 2/3 + .
  • the degradation rate of biodegradable polyester films depends on the one hand on the layer thickness of the polyester film and on the other hand on the composition of the soil in which the polyester film is to be degraded from. Polyester films over 30 ⁇ m and in particular over 50 ⁇ m generally degrade much more slowly than thinner polyester films. This is particularly problematic in low-nutrient soils or marine environments.
  • the above-mentioned nutrient salt mixture at clearly lower amounts of less than 1, 5, preferably less than 1 wt .-% nutrient salt in the polyester film already ra- see degradation rates.
  • a nutrient salt mixture is used, which necessarily has at least one nitrogen, sulfur and phosphorus-containing ion.
  • the nutrient salt mixture usually contains a cation mix.
  • the biodegradable polyester film consists essentially of a biodegradable, aliphatic or aliphatic-aromatic polyester or a biodegradable polymer mixture containing an aliphatic or aliphatic-aromatic polyester.
  • Biodegradable, aliphatic or aliphatic-aromatic (partially aromatic) polyesters consist essentially of the elements carbon (C), oxygen (O) and hydrogen (H).
  • the polyesters based on hydroxycarboxylic acids (for example polylactic acid, polyhydroxyalkanoates) and polycarbonates contained in the polymer mixtures generally also contain no nitrogen, sulfur and / or phosphorus.
  • biodegradable polyester urethanes and polyester amides contain nitrogen, this is not bioavailable, at least at the beginning of the degradation.
  • these polymers as well as their mixtures are poor sources of nutrients for microorganisms - especially in environments where nutrient deficiency is expected (low nutrient soil, marine environments, home composting).
  • polyesters based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compound so-called partially aromatic polyesters or aliphatic polyesters of aliphatic dicarboxylic acids and aliphatic diols are suitable components for the preparation of the biodegradable polyester mixtures according to the invention.
  • these polyesters Common to these polyesters is that they are biodegradable according to DIN EN 13432 and contain at least one aliphatic Ce to C2o-dicarboxylic acid.
  • mixtures of several such polyesters are suitable as component i.
  • Partly aromatic polyesters are also to be understood according to the invention as polyester derivatives, such as polyether esters, polyester amides or polyetheresteramides, and polyesterurethanes (see WO 2009/127556).
  • 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, for example, WO-A 2006/097353, WO-A 2006/097354 and WO 2010/034710.
  • semiaromatic polyesters products such as Ecoflex ® FS (BASF SE) and origo Bi ® (Novamont).
  • Particularly preferred partially aromatic polyesters include polyesters, which are essential components
  • A1) 30 to 99 mol% of at least one aliphatic dicarboxylic acid or its ester-forming derivatives or mixtures thereof, which in turn at least 70 mol% of an aliphatic
  • C1) of a compound having at least three groups capable of ester formation C2) of a di- or polyisocyanate, C3) of a di- or polyepoxide or mixtures of C1) to C3).
  • aliphatic acids and the corresponding derivatives A1 are generally those having 2 to 30 carbon atoms, preferably and at least 70 mol% of the dicarboxylic acids contain from 8 to 20 carbon atoms, into consideration. They can be both linear and branched. 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.
  • Ce to C2o-dicarboxylic acids azelaic acid, sebacic acid, brassylic acid, suberic acid (suberic acid) ,.
  • the dicarboxylic acids or their ester-forming derivatives may be used singly or as a mixture of two or more thereof.
  • azelaic acid, sebacic acid and / or brassylic acid Preference is given to using azelaic acid, sebacic acid and / or brassylic acid or their respective ester-forming derivatives or mixtures thereof. Particular preference is given to sebacin acid or their respective ester-forming derivatives or mixtures thereof.
  • Succinic acid and / or adipic acid can also be used in the mixtures. Succinic acid, azelaic acid, sebacic acid and brassylic acid also have the advantage that they are accessible from renewable raw materials.
  • polybutylene sebacate terephthalate PBSeT
  • PBAT polybutylene adipate phthalate
  • PBST polybutylene succinate terephthalate
  • the aromatic dicarboxylic acids or their ester-forming derivatives A2 may be used singly or as a mixture of two or more thereof.
  • terephthalic acid or its ester-forming derivatives such as dimethyl terephthalate used.
  • the diols B 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.
  • alkanediols examples include ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 2,4-dimethyl-2-ethylhexane-1, 3 diol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 2,2,4-trimethyl- 1, 6-hexanediol, in particular ethylene glycol, 1, 3-propanediol, 1, 4-butanediol and 2,2-dimethyl-1, 3-propanediol (neopentyl glycol); Cyclopentanediol, 1,4-cyclohexanediol, 1,2-cyclohexan
  • 1, 4-butanediol and 1, 3-propanediol are particularly preferred.
  • 1, 3 propandiol also has the advantage that it is available as a renewable resource. It is also possible to use mixtures of different alkanediols.
  • the preferred partially aromatic polyesters are characterized by a molecular weight (M n ) 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 ° C.
  • M n molecular weight
  • Polyesters of aliphatic dicarboxylic acids and aliphatic diols are understood as meaning polyesters of aliphatic diols and aliphatic dicarboxylic acids such as polybutylene succinate sebacate (PBSSe) and polybutylene sebacate (PBSe) or corresponding polyesteramides or polyesterurethanes. It is also possible to use mixtures of polysebacates with, for example, polybutylene succinate (PBS), polybutylene adipate (PBA) and / or polybutylene succinate adipate (PBSA). Suitable aliphatic polysebacates are described, for example, in WO 2010/03471 1.
  • aliphatic polyesters are obtainable by condensation of: a) 90 to 99.5 mol%, based on the components a and b, succinic acid; b) 0.5 to 10 mol%, based on the components a and b, of one or more C8-C20 dicarboxylic acids c) 98 to 102 mol%, based on the components a and b, 1, 3 propanediol or 1, 4- Butanediol and described with a viscosity number according to DIN 53728 from 100 to 450 mL / g.
  • aliphatic polyesters obtainable by condensation of: a) 90 to 99.5 mol%, based on the components a and b, succinic acid; b) 0.5 to 10 mol%, based on the components a and b, azelaic acid, sebacic acid and / or brassylic acid c) 98 to 102 mol%, based on the components a and b, 1, 3-propanediol or 1, 4th - Butanediol and d) 0.01 to 5 wt .-%, based on the total weight of components a to c, of a chain extender and / or crosslinker selected from the group consisting of: a polyfunctional isocyanate, isocyanurate, oxazoline, epoxy (in particular a e-poxide-containing poly (meth) acrylate), an at least trifunctional alcohol or an at least trifunctional carboxylic acid.
  • the polyesters in component i may also contain mixtures of aliphatic-aromatic polyesters and purely aliphatic polyesters, for example mixtures of PBSeT and PBS, PBSA or PBSSe or mixtures of PBAT and PBSSe.
  • the biodegradable polymer mixtures may contain, in addition to the abovementioned aliphatic and aliphatic / aromatic polyesters, other polymers such as, for example, polylactic acid, polyhydroxyalkanoates, polyalkylene carbonate, polycaprolactone and also inorganic and organic fillers.
  • Preferred components in the polymer blends are polylactic acid (PLA) and polyhydroxyalkanoates, and here in particular polyhydroxybutyrate (PHB) and polyhydroxybutyrate covalerate (PHBV) as well as organic fillers such as native or thermoplasticized starch.
  • PVA polylactic acid
  • PHB polyhydroxybutyrate
  • PHBV polyhydroxybutyrate covalerate
  • Polylactic acid having the following property profile is preferably used:
  • melt volume rate (MVR at 190 ° C and 2.16 kg according to ISO 1 133 of 0.5 - preferably 2 - to 30 9 ml / 10 minutes in particular a melting point below 240 ° C;
  • Tg glass transition point
  • Preferred polylactic acids are, for example, Natu re Works® 6201 D, 6202 D, 6251 D, 3051 D and in particular 4020 D or 4043D (polylactic acid from NatureWorks).
  • Polyhydroxyalkanoates are understood as meaning primarily poly-4-hydroxybutyrates and poly-3-hydroxybutyrates, and furthermore copolyesters of the abovementioned hydroxybutyrates with 3-hydroxyvalerates or 3-hydroxyhexanoate are included.
  • Poly-3-hydroxybutyrate-co-4-hydroxybutyrates are known in particular from Metabolix. They are sold under the trade name Mirel®.
  • Poly-3-hydroxybutyrate-co-3-hydroxyhexanoates are known from the company P & G or Kaneka.
  • Poly-3-hydroxybutyrates are sold, for example, by PHB Industrial under the brand name Biocycle® and by Tianan under the name Enmat®.
  • the polyhydroxyalkanoates generally have a molecular weight Mw of from 100,000 to 1,000,000, and preferably from 300,000 to 600,000.
  • Polyalkylene carbonates are understood to be primarily polyethylene carbonate (see EP-A 1264860) obtainable by copolymerization of ethylene oxide and carbon dioxide and in particular polypropylenecarbonate (see, for example, WO 2007/125039), obtainable by copolymerization of propylene oxide and carbon dioxide.
  • the polyalkylene 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. In the preferred polyalkylene carbonates, more than 85 and preferably more than 90% of all 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.
  • Polycaprolactone is marketed for example by the company. Daicel under the product names Placcel ®.
  • inorganic or organic fillers which are generally used in the range from 1 to 50% by weight and preferably from 2 to 40% by weight, based on the total weight of the polymer mixture.
  • Organic filler is understood to mean in particular: native or plastic cultured starch, natural fibers, wood flour, crushed cork, ground bark, nut shells, ground press cakes (vegetable oil refinery), dried production residues from fermentation or distillation of beverages such as beer, brewed sodas, wine or sake.
  • an inorganic filler is understood as meaning chalk, graphite, gypsum, conductive carbon black, iron oxide, dolomite, kaolin, silicon dioxide (quartz), sodium carbonate, titanium dioxide, silicate, tungstonite, mica, montmorillonites and talcum.
  • Starch and amylose may be native, i. not thermoplasticized or thermoplasticized with plasticizers such as glycerol or sorbitol (EP-A 539 541, EP-A 575 349, EP 652 910).
  • plasticizers such as glycerol or sorbitol (EP-A 539 541, EP-A 575 349, EP 652 910).
  • Natural fibers are understood as meaning cellulose fibers, hemp fibers, sisal, kenaf, jute, flax, abaca, coconut fiber or even wood flour.
  • Nutrient salt (component ii) in biology is an inorganic low-energy substance, which is necessary for producers to build up their own biomass and to take it up in ion form. They contain mineral elements such as nitrogen, sulfur or phosphorus.
  • Component ii denotes 0.01 to 1.5% by weight of a nutrient salt mixture comprising: a) at least one nitrogen-containing cation or anion,
  • Component ii is used in 0.01 to 1, 5 wt .-%, preferably 0.1 to 1 wt .-% based on the polyester or the polyester mixture.
  • the nutrient salts preferably contain at least one cation and more preferably at least two cations selected from the group Na + , K + , Ca 2+ , Mg 2+ and Fe 2 3+ .
  • the nitrogen-containing ion a) is in particular NH 4 + (ammonium) and / or the anions N0 3 " (nitrate) or NO 2 " (nitrite).
  • Nitrogen-containing salts are contained in the nutrient salt mixture usually in 5 to 70 wt .-% and preferably 10 to 60 wt .-%. Ammonium ions are particularly preferred nitrogen-containing ions.
  • Sulfur-containing ion b) is in particular S0 4 2_ (sulfate) and HSO 4 " (hydrogen sulfate) in question
  • Sulfur-containing salts in the nutrient salt mixture are generally in 5 to 70% by weight and preferably 10 contain up to 60 wt .-%.
  • Phosphorus-containing ions c) are, for example, P0 4 3 ⁇ (phosphate), HP0 4 2 " (hydrogen phosphate), and H 2 P0 4 - (dihydrogenphosphate).
  • Phosphorus-containing salts are generally present in the nutrient salt mixture in 5 to 70% by weight .-%, and preferably 10 to 60 wt .-% included.
  • Preferred salts are NaCl, KCl, CaCl 2, MgCl 2 * 6H 2 0, NH 4 Cl, Na 2 S0 4, K 2 S0 4, NaHS0 4, KHS0 4 , NH 4 Cl, (NH 4 ) 2 SO 4 , (NH 4 ) 3 PO 4 .
  • biodegradable for a substance or a substance mixture is fulfilled if this substance or the substance mixture according to DIN EN 13432 has a percentage degree of biodegradation of at least 90%.
  • biodegradability causes the polyester (mixtures) to decompose 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 is usually effected for the most part 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), C0 2 -free air is allowed to flow through ripened compost during composting and subjected to a defined temperature program.
  • biodegradability is determined by the ratio of the net C0 2 release of the sample (after deduction of C0 2 release by the compost without sample) to the maximum C0 2 release of the sample (calculated from the carbon content of the sample) as a percentage defined as biodegradation.
  • Biodegradable polyesters mixtures usually show clear degradation phenomena such as fungal growth, cracking and hole formation after only a few days of composting.
  • the aforementioned films containing biodegradable polyester and polyester mixtures are suitable for the production of nets and fabrics, tubular films, chill-roll films with and without orientation in a further process step, with and without metallization or SiOx coating.
  • the films mentioned above containing the components i and ii are suitable for tubular films and stretch films.
  • Possible applications here are bottom folding bags, side bags, handle bags, shrink labels or shirt carrier bags, inliners, heavy bags, freezer bags, composting bags, agricultural films (mulch films), film bags for food packaging, removable sealing film - transparent or opaque - weldable sealing film - transparent or opaque -, sausage casing, salad foil, plastic wrap (stretch film) for fruit and vegetables, meat and fish, stretch film for wrapping pallets, film for nets, packaging films for snacks, chocolate and cereal bars, peelable lidding films for dairy packaging (yoghurt, cream etc.), fruit and vegetables, semi-hard packaging for smoked sausage and cheese.
  • the films mentioned are predestined for packaging meat, poultry, meat products, processed meat, sausages, smoked sausage, seafood, fish, crabmeat, cheese, cheese products, desserts, pies z.
  • meat, fish, poultry, tomato stuffing, pastes and spreads Bread, cakes, other baked goods; Fruit, fruit juices, vegetables, tomato paste, salads; Pet food; pharmaceutical products; Coffee, coffee-based products; Milk or cocoa powder, coffee whitener, baby food; dried foods; Jams and jellies; Spreads, chocolate cream; Ready meals.
  • Food Processing Handbook James G Brennan, Wiley-VCH, 2005.
  • polyester films according to the invention generally have a layer thickness of 5 to 500 ⁇ m and in particular 25 to 400 ⁇ m from 25 to 50 ⁇ m and for composting pouches layer thicknesses of 10 to 30 ⁇ m mulch foils generally have layer thicknesses of 8 to 30 ⁇ m and foils / plates obtained by thermoforming can be up to 500 ⁇ m thick.
  • polyester films according to the invention are particularly suitable for agricultural applications such as mulch films or composting applications such as composting bags or shopping bags, which are used after purchase as organic waste bag (composting bag).
  • composting bags or shopping bags which are used after purchase as organic waste bag (composting bag).
  • composting bags or shopping bags which are used after purchase as organic waste bag (composting bag).
  • Inliners in biowaste bins can be produced advantageously from the polyester films according to the invention.
  • Conventional films often have the problem in the abovementioned applications that they are not degraded quickly enough or not completely enough in composting plants or biogas plants or in arable land. This is especially true for films of a thickness greater than 30 and in particular greater than 50 ⁇ . In agricultural applications such as mulching films, the degradation of conventional polyester films in nutrient-poor soils is often slowed down.
  • polyester films according to the invention degrade much faster than conventional polyester films and are therefore very well suited for the abovementioned applications.
  • polyester i-1 had a melting temperature of 1 19 ° C and a molecular weight (M n ) of 23000 g / mol.
  • the chain extension was carried out in a Haake Kneader Rheocord 9000 with a Rheomix 600 attachment.
  • the prepolyester was melted at 220 ° C and the melt added dropwise with 0.6 wt .-% of HDI (hexamethylene diisocyanate).
  • the progress of the reaction was monitored by observing the torque.
  • the reaction mixture was cooled after reaching maximum torque, and the chain-extended, biodegradable polyester was removed and characterized.
  • Butanediol (87.5 g, 130 mol%), succinic acid (79.4 g, 90 mol%) and sebacic acid (15.1 g, 10 mol%) were initially heated to 200 ° C. in the presence of TBOT (0.2 g). The melt was held at this temperature for 80 minutes. Subsequently, at reduced pressure ( ⁇ 5 mbar) and a maximum internal temperature of 250 ° C., 1, 4-butanediol was distilled off. The polyester was poured out and analyzed after cooling. The polyester obtained had a viscosity number of 252 ml / g.
  • Comparative Example V-8 P3 was melted in a Midiextruder and compounded with 2 wt .-% of the salt mixture S2.
  • Example 1 The compounds described above (Examples 1 to 8) were pressed into films of a thickness of 400 ⁇ m. The plates were cut into 4 x 1 cm rectangular pieces. These were buried in a plastic box in fresh compost, the moisture was adjusted by adding water and incubated at 58 ° C. Samples were taken regularly, cleaned under running water, dried at 60 ° C overnight in vacuo and the mass difference to the mass determined at the start time. The relative rate of degradation relative to the surface of the rectangular polymer strip was compared.

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)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une feuille de polyester biodégradable contenant : i) de 99,99 à 98,50 % en poids d'un polyester à partir d'acides dicarboxyliques aliphatiques et/ou aromatiques, au moins l'un des acides dicarboxyliques étant un acide dicarboxylique aliphatique en C8 à C20, et de diols aliphatiques ou d'un mélange de polymères biodégradable contenant un tel polyester et ii) de 0,01 à 1,50 % en poids d'un mélange de sels nutritifs contenant : a) au moins un cation ou anion contenant de l'azote, b) au moins un anion contenant du soufre et c) au moins un anion contenant du phosphore, d) au moins un cation choisi parmi le groupe comprenant : K+, Na+, Ca2+, Mg2+ et Fe2/3+.
PCT/EP2012/052841 2011-02-23 2012-02-20 Feuille de polyester contenant des sels nutritifs WO2012113744A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11155596 2011-02-23
EP11155596.7 2011-02-23

Publications (1)

Publication Number Publication Date
WO2012113744A1 true WO2012113744A1 (fr) 2012-08-30

Family

ID=44009980

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/052841 WO2012113744A1 (fr) 2011-02-23 2012-02-20 Feuille de polyester contenant des sels nutritifs

Country Status (1)

Country Link
WO (1) WO2012113744A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014075997A1 (fr) * 2012-11-15 2014-05-22 Basf Se Mélange de polyesters biodégradable
CN107459784A (zh) * 2016-12-13 2017-12-12 金发科技股份有限公司 一种可生物降解聚酯组合物
WO2020115221A1 (fr) 2018-12-06 2020-06-11 Basf Se Procédé de production d'un (co)polyester

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4789727A (en) 1987-12-18 1988-12-06 Arco Chemical Company Reduction of catalyst usage in epoxide/CO2 polymerization
WO1992009654A2 (fr) 1990-11-30 1992-06-11 Eastman Kodak Company Melanges de copolyesters aliphatiques aromatiques et d'esters/de polymeres de cellulose
EP0539541A1 (fr) 1991-05-03 1993-05-05 Novamont Spa Compositions polymeres biodegradables a base d'amidon et de polymeres thermoplastiques.
EP0575349A1 (fr) 1991-02-20 1993-12-29 NOVAMONT S.p.A. Compositions polymeres biodegradables a base d'amidon et de polymeres thermoplastiques
EP0652910A1 (fr) 1992-08-03 1995-05-17 NOVAMONT S.p.A. Composition polymere biodegradable
JPH11113414A (ja) * 1997-10-17 1999-04-27 Mitsui Chem Inc 成形加工品
DE19754063A1 (de) * 1997-12-05 1999-06-10 Bayer Ag Abbau von biologisch abbaubaren Polymeren
JP2002212830A (ja) * 2001-01-11 2002-07-31 Unitika Ltd 生分解性ポリエステル繊維
US20020123546A1 (en) * 1988-08-08 2002-09-05 Ecopol, Llc Degradation control of environmentally degradable disposable materials
EP1264860A1 (fr) 2000-08-02 2002-12-11 Mitsui Chemicals, Inc. Composition de resine et utilisation de celle-ci
EP1582095A1 (fr) 2004-04-01 2005-10-05 ARGUS Additive Plastics GmbH Matériau biodégradable
WO2006097354A1 (fr) 2005-03-18 2006-09-21 Novamont S.P.A. Polyester aromatique-aliphatique biodegradable
WO2007125039A1 (fr) 2006-04-27 2007-11-08 Basf Se Mélanges transparents de carbonate de polypropylène
US7304172B2 (en) 2004-10-08 2007-12-04 Cornell Research Foundation, Inc. Polycarbonates made using highly selective catalysts
WO2009127556A1 (fr) 2008-04-15 2009-10-22 Basf Se Procédé de production en continu de polyesters biodégradables
WO2010034710A1 (fr) 2008-09-29 2010-04-01 Basf Se Polyester aliphatique-aromatique
WO2010034711A1 (fr) 2008-09-29 2010-04-01 Basf Se Polyesters aliphatiques
DE102008051579A1 (de) 2008-10-14 2010-04-15 Rhodia Acetow Gmbh Biologisch abbaubarer Kunststoff und Verwendung desselben

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4789727A (en) 1987-12-18 1988-12-06 Arco Chemical Company Reduction of catalyst usage in epoxide/CO2 polymerization
US20020123546A1 (en) * 1988-08-08 2002-09-05 Ecopol, Llc Degradation control of environmentally degradable disposable materials
WO1992009654A2 (fr) 1990-11-30 1992-06-11 Eastman Kodak Company Melanges de copolyesters aliphatiques aromatiques et d'esters/de polymeres de cellulose
EP0575349A1 (fr) 1991-02-20 1993-12-29 NOVAMONT S.p.A. Compositions polymeres biodegradables a base d'amidon et de polymeres thermoplastiques
EP0539541A1 (fr) 1991-05-03 1993-05-05 Novamont Spa Compositions polymeres biodegradables a base d'amidon et de polymeres thermoplastiques.
EP0652910A1 (fr) 1992-08-03 1995-05-17 NOVAMONT S.p.A. Composition polymere biodegradable
JPH11113414A (ja) * 1997-10-17 1999-04-27 Mitsui Chem Inc 成形加工品
DE19754063A1 (de) * 1997-12-05 1999-06-10 Bayer Ag Abbau von biologisch abbaubaren Polymeren
EP1264860A1 (fr) 2000-08-02 2002-12-11 Mitsui Chemicals, Inc. Composition de resine et utilisation de celle-ci
JP2002212830A (ja) * 2001-01-11 2002-07-31 Unitika Ltd 生分解性ポリエステル繊維
EP1582095A1 (fr) 2004-04-01 2005-10-05 ARGUS Additive Plastics GmbH Matériau biodégradable
US7304172B2 (en) 2004-10-08 2007-12-04 Cornell Research Foundation, Inc. Polycarbonates made using highly selective catalysts
WO2006097353A1 (fr) 2005-03-18 2006-09-21 Novamont S.P.A. Polyesters aliphatiques/aromatiques biodegradables
WO2006097354A1 (fr) 2005-03-18 2006-09-21 Novamont S.P.A. Polyester aromatique-aliphatique biodegradable
WO2007125039A1 (fr) 2006-04-27 2007-11-08 Basf Se Mélanges transparents de carbonate de polypropylène
WO2009127556A1 (fr) 2008-04-15 2009-10-22 Basf Se Procédé de production en continu de polyesters biodégradables
WO2010034710A1 (fr) 2008-09-29 2010-04-01 Basf Se Polyester aliphatique-aromatique
WO2010034711A1 (fr) 2008-09-29 2010-04-01 Basf Se Polyesters aliphatiques
DE102008051579A1 (de) 2008-10-14 2010-04-15 Rhodia Acetow Gmbh Biologisch abbaubarer Kunststoff und Verwendung desselben

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 30 April 1999 (1999-04-30), OFUCHI, SHOJI ET AL: "Biodegradable aliphatic polyester molded products, their manufacturing process, and their uses", XP002640005, retrieved from STN Database accession no. 1999:267065 *
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 31 July 2002 (2002-07-31), MATSUOKA, FUMIO ET AL: "Biodegradable polyester fibers with good tensile strength and soft handle consisting of polyester compositions containing soil nutrient salts", XP002640006, retrieved from STN Database accession no. 2002:566473 *
DATABASE WPI Week 200379, Derwent World Patents Index; AN 2003-847053, XP002638368 *
JAMES G. BRENNAN: "Food Processing Handbook", 2005, WILEY-VCH
SOGA ET AL., POLYMER JOURNAL, vol. 13, 1981, pages 407 - 10

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014075997A1 (fr) * 2012-11-15 2014-05-22 Basf Se Mélange de polyesters biodégradable
WO2014075998A1 (fr) * 2012-11-15 2014-05-22 Basf Se Mélange polyester biodégradable
CN104837923A (zh) * 2012-11-15 2015-08-12 巴斯夫欧洲公司 生物可降解的聚酯混合物
CN104837923B (zh) * 2012-11-15 2018-01-02 巴斯夫欧洲公司 生物可降解的聚酯混合物
US10526461B2 (en) 2012-11-15 2020-01-07 Basf Se Biodegradable polyester mixture
CN107459784A (zh) * 2016-12-13 2017-12-12 金发科技股份有限公司 一种可生物降解聚酯组合物
WO2018107970A1 (fr) * 2016-12-13 2018-06-21 金发科技股份有限公司 Composition de polyester biodégradable
CN107459784B (zh) * 2016-12-13 2020-05-19 金发科技股份有限公司 一种可生物降解聚酯组合物
WO2020115221A1 (fr) 2018-12-06 2020-06-11 Basf Se Procédé de production d'un (co)polyester

Similar Documents

Publication Publication Date Title
EP2331634B1 (fr) Melanges de polymeres biodegradables
EP2920245B1 (fr) Mélange de polyester biodégradable
DE60200881T2 (de) Ternäre mischung biologisch abbaubarer polyester und damit erhaltene produkte
EP0792309B1 (fr) Polymeres biodegradables, leur procede de production et leur utilisation pour la fabrication de corps moules biodegradables
EP2331603B1 (fr) Polyesters aliphatiques-aromatiques
US20110237750A1 (en) Process for film production
EP0792312A1 (fr) Polymeres biodegradables, leur procede de production et leur utilisation pour la fabrication de corps moules biodegradables
EP2550329B1 (fr) Procédé pour la préparation des films
WO1996015175A1 (fr) Polymeres biodegradables, leur procede de production et leur utilisation pour la fabrication de corps moules biodegradables
WO2011117265A1 (fr) Procédé de réalisation de films adhésifs
EP0792310A1 (fr) Polymeres biodegradables, leur procede de production et leur utilisation pour la fabrication de corps moules biodegradables
EP0802942A1 (fr) Polymeres biodegradables, leur procede de production et leur uti lisation pour la production de corps moules biodegradables
US20110237743A1 (en) Process for producing clingfilms
WO2012113744A1 (fr) Feuille de polyester contenant des sels nutritifs
WO1996007687A1 (fr) Polyester biodegradable et materiau fabrique en un tel polyester
WO2016087372A1 (fr) Polyester biodégradable
WO2012126921A1 (fr) Polyester à base d'acide 2-méthylsuccinique
CN104428369B (zh) 聚合物混合物的完全厌氧消化的方法
WO2014009176A1 (fr) Procédé de biodégradation anaérobie complète de mélanges polymères

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12704809

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12704809

Country of ref document: EP

Kind code of ref document: A1