WO2011117265A1 - Procédé de réalisation de films adhésifs - Google Patents

Procédé de réalisation de films adhésifs Download PDF

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Publication number
WO2011117265A1
WO2011117265A1 PCT/EP2011/054386 EP2011054386W WO2011117265A1 WO 2011117265 A1 WO2011117265 A1 WO 2011117265A1 EP 2011054386 W EP2011054386 W EP 2011054386W WO 2011117265 A1 WO2011117265 A1 WO 2011117265A1
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Prior art keywords
acid
components
mol
iii
dicarboxylic
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PCT/EP2011/054386
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German (de)
English (en)
Inventor
Liqun Ren
Gabriel Skupin
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Basf Se
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Priority to EP11709426A priority Critical patent/EP2550330A1/fr
Priority to CA2792845A priority patent/CA2792845A1/fr
Priority to AU2011231669A priority patent/AU2011231669A1/en
Priority to CN2011800155350A priority patent/CN102869723A/zh
Priority to KR1020127027563A priority patent/KR20130010080A/ko
Publication of WO2011117265A1 publication Critical patent/WO2011117265A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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

Definitions

  • the present invention relates to a process for the production of cling foils using biodegradable polyesters obtainable by polycondensation of:
  • dicarboxylic acid derivatives or dicarboxylic acids selected from the group consisting of: succinic acid, adipic acid, sebacic acid, azelaic acid and hydrosilicic acid;
  • the invention relates to a process for the preparation of cling foils using the polymer components a) and b):
  • the invention relates to a process for the production of cling foils using the polymer components a), b) and c): a) 10 to 40 wt .-% of a biodegradable polyester according to claim 1 and
  • an aliphatic-aromatic polyester obtainable by polycondensation of: i) 40 to 70 mol%, based on components i to ii, of one or more dicarboxylic acid derivatives or dicarboxylic acids selected from the group consisting of: Succinic, adipic, sebacic, azelaic and brassylic acids; ii) 60 to 30 mol%, based on the components i to ii, of a terephthalic acid derivative; iii) 98 to 102 mol%, based on components i to ii, of a C 2 -C 8 -alkylenediol or C 2 -C 6 -oxyalkylenediol; iv) 0 to 2% by weight, based on the polymer obtainable from components i to iii, of an at least trifunctional crosslinker or difunctional chain extender;
  • polymers selected from the group consisting of: polylactic acid, polycaprolactone, polyhydroxyalkanoate, polyalkylene lencarbonat, chitosan and gluten and one or more polyesters based on aliphatic diols and aliphatic dicarboxylic - and
  • WO-A 92/09654 describes linear aliphatic-aromatic polyesters which are biodegradable. Crosslinked, biodegradable polyesters are described in WO-A 96/15173. The polyesters described have a higher terephthalic acid content and can not always convince with regard to their film properties - in particular their elastic behavior, which is of great importance for cling film. The aim of the present invention was therefore to provide a process for the production of cling foils.
  • polyesters described at the outset which have a narrowly defined terephthalic acid content and a narrowly defined content of crosslinking agent, are surprisingly very suitable for cling film.
  • biodegradable polyesters having the following constituents: Components i) is preferably adipic acid and / or sebacic acid. Component iii), the diol, is preferably 1,4-butanediol. Component iv), the crosslinker, is preferably glycerol.
  • the synthesis of the polyesters described is generally carried out in a two-stage reaction cascade (see WO09 / 127555 and WO09 / 127556).
  • the dicarboxylic acid derivatives as in the synthesis examples, are reacted together with the diol (for example 1,4-butanediol) in the presence of a transesterification catalyst to give a prepolyester.
  • This prepolyester generally has a viscosity number (CV) of 50 to 100 ml / g, preferably 60 to 90 ml / g.
  • the catalysts used are usually zinc, aluminum and in particular titanium catalysts.
  • Titanium catalysts such as tetra (isopropyl) orthotitanate and in particular tetrabutyl orthotitanate (TBOT) have the advantage over the tin, antimony, cobalt and lead catalysts commonly used in the literature, such as tin dioctanoate, that residual amounts of the catalyst or secondary product of the catalyst remaining in the product are less toxic are.
  • TBOT tetrabutyl orthotitanate
  • the polyesters according to the invention are optionally subsequently chain-extended according to the processes described in WO 96/15173 and EP-A 488 617.
  • the prepolyester is reacted, for example, with chain extenders vib), as with diisocyanates or with epoxy-containing polymethacrylates, in a chain extension reaction to give a polyester having a viscosity of 60 to 450 ml / g, preferably 80 to 250 ml / g.
  • a mixture of the dicarboxylic acids is initially condensed in the presence of an excess of diol together with the catalyst initially.
  • the melt of the prepolyester thus obtained is usually at an internal temperature of 200 to 250 ° C within 3 to 6 hours at reduced pressure while distilling off diols to the desired viscosity with a viscosity number (VZ) of 60 to 450 mL / g and preferably 80 to 250 mL / g condensed.
  • VZ viscosity number
  • the polyesters according to the invention can also be prepared in a batch process.
  • the aliphatic and the aromatic dicarboxylic acid derivative, the diol and a branching agent are mixed in any metering order and condensed to form a prepolyester.
  • a polyester can be adjusted with the desired viscosity number.
  • polybutylene terephthalate succinates, azelates, brassates and, in particular, adipates and sebacates having an acid number, measured in accordance with DIN EN 12634, of less than 1.0 mg KOH / g and a viscosity number greater than 130 ml / g can be obtained by the abovementioned processes and a MVR according to ISO 1133 of less than 6 cm 3/10 min (190 ° C, 2.16 kg weight). These products are particularly interesting for film applications.
  • Sebacic acid, azelaic acid and brassylic acid (i) are derived from renewable resources, in particular from vegetable oils such as e.g. Castor oil accessible.
  • the terephthalic acid ii is used in 20 to 35 mol%, based on the acid components i and ii.
  • Terephthalic acid and the aliphatic dicarboxylic acid can be used either as the free acid or in the form of ester-forming derivatives.
  • Particularly suitable ester-forming derivatives are the di-C 1 - to C 6 -alkyl esters, such as dimethyl, diethyl, di-n-propyl, diisopropyl, di-n-butyl, diisobutyl, di-t-butyl, Di-n-pentyl, di-iso-pentyl or di-n-hexyl esters to name.
  • Anhydrides of dicarboxylic acids can also be used.
  • the dicarboxylic acids or their ester-forming derivatives can be used individually or as a mixture.
  • 09/024294 discloses a biotechnological process for the production of 1,4-butanediol from different carbohydrates with microorganisms from the class of Pasteurellaceae.
  • the diol (component iii) is added to the acids (components i and ii) in a ratio of diol to diacids of from 1.0 to 2.5: 1 and preferably from 1.3 to 2.2: l set.
  • Excess diol quantities are withdrawn during the polymerization, so that at the end of the polymerization an approximately equimolar ratio is established.
  • approximately equimolar is meant a diol / diacid ratio of 0.98 to 1.02: 1.
  • the said polyesters may have hydroxyl and / or carboxyl end groups in any ratio.
  • the abovementioned partially aromatic polyesters can also be end-group-modified.
  • OH end groups can be acid-modified by reaction with phthalic acid, phthalic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic acid or pyromellitic anhydride. Preference is given to polyesters having acid numbers of less than 1.5 mg KOH / g.
  • a crosslinker iva and optionally additionally a chain extender ivb selected from the group consisting of: a polyfunctional isocyanate, isocyanurate, oxazoline, epoxide, carboxylic anhydride, an at least trifunctional alcohol or an at least trifunctional carboxylic acid are used.
  • Suitable chain extenders ivb are polyfunctional and in particular difunctional isocyanates, isocyanurates, oxazolines, carboxylic anhydride or epoxides.
  • the crosslinkers iva are generally in a concentration of 0.1 to 2 wt .-%, preferably 0.2 to 1, 5 wt .-% and particularly preferably 0.3 to 1 wt .-% based on the polymer available from components i to iii used.
  • the chain extenders ivb) are generally used in a concentration of 0.01 to 2 wt .-%, preferably 0.1 to 1 wt .-% and particularly preferably 0.35 to 2 wt .-% based on the total weight of the components i used to iii.
  • Chain extenders and alcohols or carboxylic acid derivatives having at least three functional groups can also be understood as crosslinkers.
  • Particularly preferred compounds have three to six functional groups. Examples include: tartaric acid, citric acid, malic acid; Trimethylolpropane, trimethylolethane; pentaerythritol; Polyether triols and glycerol, trimesic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid and pyromellitic dianhydride. Preference is given to polyols such as trimethylolpropane, pentaerythritol and in particular glycerol.
  • biodegradable polyesters with a structural viscosity can be built up.
  • the rheological behavior of the melts improves;
  • the biodegradable polyesters are easier to process, for example, better by melt consolidation to remove films.
  • the compounds iv are shear-thinning, i. the viscosity under load becomes lower.
  • Suitable bifunctional chain extenders are aromatic diisocyanates and in particular aliphatic diisocyanates, especially linear or branched alkylene diisocyanates or cycloalkylene diisocyanates having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, eg 1, 6-hexa-methylene diisocyanate, isophorone diisocyanate or methylene bis (4- isocyanatocyclo-hexane).
  • Particularly preferred aliphatic diisocyanates are isophorone diisocyanate and in particular 1,6-hexamethylene diisocyanate.
  • the polyesters of the invention generally have a number average molecular weight (Mn) in the range from 5000 to 100,000, in particular in the range from 10,000 to 60,000 g / mol, preferably in the range from 15,000 to 38,000 g / mol, a weight-average molecular weight (Mw) from 30,000 to 300,000, preferably 60,000 to 200,000 g / mol, and a Mw / Mn ratio of 1 to 15, preferably 2 to 8.
  • the viscosity number is between 30 and 450, preferably from 50 to 400 ml / g and in particular preferably from 80 to 250 ml / g (measured in o-dichlorobenzene / phenol (weight ratio 50/50)).
  • the melting point is in the range of 85 to 150, preferably in the range of 95 to 140 ° C.
  • an organic filler is selected from the group consisting of: native or plasticized starch, natural fibers, wood flour, comminuted cork, ground bark, Nutshells, ground press cakes (vegetable oil refinery), dried production residues from the fermentation or distillation of beverages such as Beer, brewed sodas (eg bionade), wine or sake and / or an inorganic filler selected from the group consisting of: chalk, graphite, gypsum, carbon black, iron oxide, calcium chloride, dolomite, kaolin, silicon dioxide (quartz), sodium carbonate, titanium dioxide, Silicate, wollastonite, mica, montmorillonite, talc, glass fibers and mineral fibers added.
  • Starch and amylose may be native, i. not thermoplasticized or thermoplasticized with plasticizers such as glycerol or sorbitol (EP-A 539 541, EP-A
  • Natural fibers are, for example, cellulose fibers, hemp fibers, sisal, kenaf, Jute, Flax, Abacca, coconut fiber or regenerated cellulose fibers (rayon) such.
  • cellulose fibers for example, hemp fibers, sisal, kenaf, Jute, Flax, Abacca, coconut fiber or regenerated cellulose fibers (rayon) such.
  • Ceisal for example, hemp fibers, sisal, kenaf, Jute, Flax, Abacca, coconut fiber or regenerated cellulose fibers (rayon) such.
  • Preferred fibrous fillers are glass fibers, carbon fibers, aramid fibers, potassium titanate fibers and natural fibers, glass fibers being particularly preferred as E glass. These can be used as rovings or in particular as chopped glass in the commercial forms. These fibers generally have a diameter of 3 to 30 ⁇ , preferably 6 to 20 ⁇ and special preferably from 8 to 15 ⁇ on.
  • the fiber length in the compound is generally 20 ⁇ to ⁇ ⁇ , preferably 180 to 500 ⁇ and more preferably 200 to 400 ⁇ .
  • the fibrous fillers can be surface-pretreated for better compatibility with the thermoplastic, for example with a silane compound.
  • the biodegradable polyester or polyester mixtures may contain further ingredients known to the person skilled in the art but not essential to the invention.
  • the customary in plastics technology additives such as stabilizers;
  • Plasticizers such as citric acid esters (especially acetyl tributyl citrate), glyceric acid esters such as triacetylglycerol or ethylene glycol derivatives, surfactants such as polysorbates, palmitates or laurates; Waxes such as beeswax or beeswax esters; Antistatic, UV absorber; UV-stabilizer; Antifog agents or dyes.
  • the additives are used in concentrations of 0 to 5 wt .-%, in particular 0.1 to 2 wt .-% based on the polyesters of the invention. Plasticizers may be present in 0.1 to 10% by weight in the polyesters of the invention.
  • the biodegradable polyesters of claim 1 are often tacky. In order to accomplish their processing into films without problems, it is advisable, if the polyesters are to be used without further mixing partners, to add additives such as, in particular, lubricants and release agents.
  • lubricants or mold release agents are in particular hydrocarbons, fatty alcohols, higher carboxylic acids, metal salts of higher carboxylic acids such as calcium or zinc stearate, fatty acid amides such as erucic acid amide and wax types, z.
  • lubricants are erucic acid amide and / or wax types, and more preferably combinations of these lubricants.
  • Preferred types of wax are beeswax and Esterwachse, in particular glycerol monostearate or dimethylsiloxane or polydimethylsiloxane such as Belsil ® DM Fa. Wacker.
  • the component e is usually added in 0.05 to 5.0 wt .-% and preferably 0.1 to 2.0 wt .-% based on the biodegradable polyester.
  • a preferred formulation of the biodegradable polyester comprises: a) 99.9 to 98% by weight of an aliphatic-aromatic polyester obtainable by polycondensation of: 65 to 80 mol%, based on the components i to ii, of one or more dicarboxylic acid derivatives or dicarboxylic acids selected from the group consisting of: succinic acid, adipic acid, sebacic acid, azelaic acid and brassylic acid;
  • a lubricant or release agent 0.1 to 2 wt .-% of a lubricant or release agent.
  • Preference is furthermore Clingfolien containing the aforementioned formulations.
  • Typical polyester mixtures for cling film preparation contain: a) 5 to 95% by weight, preferably 10 to 40% by weight and particularly preferably 25 to 35% by weight of a biodegradable polyester according to Claim 1 and b) 95 to 50% by weight. %, preferably 90 to 60 wt .-% and particularly preferably 75 to 65 wt .-% of an aliphatic-aromatic polyester obtainable by polycondensation of: i) 40 to 60 mol%, based on the components i to ii, of one or a plurality of dicarboxylic acid derivatives or dicarboxylic acids selected from the group consisting of: succinic acid, adipic acid, sebacic acid, azelaic acid and brassylic acid; ii) 60 to 40 mol%, based on the components i to ii, of a terephthalic acid derivative; iii) 98 to 102 mol%, based on components i to ii, of
  • polymer mixtures are suitable for the production of cling foils: a) 10 to 40% by weight, preferably 20 to 30% by weight, of a biodegradable polyester according to claim 1 and
  • Alkylenediols or C 2 -C 6 -oxyalkylenediols vi) 0 to 2 wt .-%, based on the polymer obtainable from the components to iii, of an at least trifunctional crosslinker or difunctional Ketten tenverinaterers;
  • a compatibilizer 0 to 2 wt .-% of a compatibilizer.
  • the aforementioned polyester mixtures comprising the components a) and b) or a), b) and c) are suitable as Clingfolien due to their excellent recovery behavior.
  • the polymer mixtures in turn preferably contain from 0.05 to 2% by weight of a compatibilizer.
  • Preferred compatibilizers are carboxylic acid anhydrides, such as maleic anhydride, and in particular the previously described epoxide group-containing copolymers based on styrene, acrylic esters and / or methacrylic acid esters.
  • the epoxy groups bearing units are preferably glycidyl (meth) acrylates.
  • the epoxy-containing copolymers of the above type are sold for example by BASF Resins BV under the trademark Joncryl ® ADR. Is particularly suitable as compatibilizers, for example, Joncryl ADR ® 4368.
  • As a biodegradable polyester (component b) is suitable, for example, re Polymilchkla-.
  • Polylactic acid having the following property profile is preferably used:
  • a melt volume rate (MVR at 190 ° C. and 2.16 kg according to ISO 1 133 of 0.5 to 30, preferably 2 to 18 ml / 10 minutes)
  • Preferred polylactic acids are, for example, NatureWorks® 3001, 3051, 3251, 4020, 4032 or 4042D (polylactic acid from NatureWorks or NL-Naarden and USA Blair / Kansas).
  • Polyhydroxyalkanoates are understood as meaning primarily poly-4-hydroxybutyrates and poly-3-hydroxybutyrates, 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.
  • Polycaprolactone is marketed by the company. Daicel under the product names Placcel ®.
  • Polyalkylene carbonates are understood as meaning, in particular, polyethylene carbonate and polypropylene propylene carbonate.
  • Partly aromatic (aliphatic-aromatic) polyesters based on aliphatic diols and aliphatic / aromatic dicarboxylic acids (component c) are also understood to mean polyester derivatives such as polyether esters, polyester amides or polyetherresteramides.
  • Suitable partially aromatic polyesters include linear non-chain-extended polyesters (WO 92/09654).
  • aliphatic / aromatic polyesters of butanediol, terephthalic acid and aliphatic C6-Ci8 dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid and brassylic acid (for example as described in WO 2006/097353 to 56) suitable mixing partners.
  • Preferred are chain-extended and / or branched partially aromatic polyesters. The latter are known from the aforementioned documents 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.
  • 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 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 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), C02-free air is allowed to flow through matured compost during composting and subjected to a defined temperature program.
  • the biodegradability is determined by the ratio of the net CO 2 release of the sample (after subtraction 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 the CO 2 release defined 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.
  • the Clingfolien (cling film) are generally produced in the thickness range of 10 to 25 ⁇ .
  • the usual manufacturing process is the tubular film extrusion in a monolayer film.
  • chill-roll extrusion has also established itself as a process for coextruded cling films.
  • the cling foils hitherto on the market consist mainly of PVC, plasticizers (e.g., 20-30% dioctyl phthalate), and anti-fog additives which prevent the film from fogging during temperature cycling.
  • plasticizers e.g., 20-30% dioctyl phthalate
  • anti-fog additives which prevent the film from fogging during temperature cycling.
  • cling foils based on LDPE have prevailed, but they require a clinging additive (polyisobutylene).
  • Cling foils made of PE also contain anti-fog additives.
  • a specific version of the cling foil contains a styrene / butadiene copolymer (styroflex), which has excellent recovery on deformation. These films are produced in 3 layers. The outer layers contain an ethylenevinyl acetate, which is equipped with antifogging additives. The middle layer contains the styrene / butadiene copolymer which provides strength, extensibility and resilience. Cling foils are used for the packaging of fruits and vegetables as well as fresh meat, bones and fish. You have the following requirement profile:
  • Films of biodegradable polyester according to claim 1 have good film properties and can be very good to 10 ⁇ undress.
  • the mechanical properties such as longitudinal and transverse strength for extrusion and puncture resistance are at a high level.
  • Tubular films made from these polyesters show a highly elastomeric behavior. They achieve higher strengths than PVC before the film breaks. Therefore, one is Modification of the stiffness-toughness ratio by the use of branching agents and the reduction of the terephthalic acid content for Clingfolien useful.
  • Cling foils made from these polyesters can also be equipped with anti-fog additives. The transparency of these cling foils is sufficient for most applications. However, they are not quite as transparent as PVC and therefore distinguishable from traditional PVC.
  • the Clingfolien invention impressed by the improved hysteresis (resilience of deformations).
  • the cling foils of the present invention are also easier to cut without tearing longitudinally to the direction of extrusion, since with lower terephthalic acid content and increased branching, the strong anisotropy of the film is reduced.
  • the weldability of the cling foils of the invention is at a similar level as PVC or PE.
  • the molecular weights Mn and Mw of the semiaromatic polyesters were determined in accordance with DIN 55672-1 eluent hexafluoroisopropanol (HFIP) + 0.05% by weight of trifluoroacetic acid potassium salt; The calibration was carried out with narrowly distributed polymethyl methacrylate standards. The determination of the viscosity numbers was carried out according to DIN 53728 Part 3, January 3, 1985, capillary viscometry. A micro Ubbelohde viscometer, type M-II was used. The solvent used was the mixture: phenol / o-dichlorobenzene in a weight ratio of 50/50.
  • the hysteresis test was carried out on 60 ⁇ thick films according to DIN 53835 at 23 ° C. The film was first loaded at 120 mm / min. After reaching the 50% elongation was relieved without holding time again. Then was waited for 5 minutes. This was followed by the second cycle with 100% stretch in the top.
  • the degradation rates of the biodegradable polyester blends and the blends prepared for comparison were determined as follows:
  • films having a thickness of 30 ⁇ m were produced by pressing at 190 ° C. These films were each cut into square pieces with edge lengths of 2 x 5 cm. The weight of these pieces of film was determined in each case and defined as "100% by weight.” Over a period of four weeks, the pieces of film were heated to 58 ° C. in a drying box in a plastic can filled with humidified compost remain- Bending weight of the film pieces measured and converted to wt .-% (based on the determined at the beginning of the test and defined as "100 wt .-%" weight).
  • a polybutylene terephthalate adipate prepared as follows: 1, 10.1 g of dimethyl terephthalate (27 mol%), 224 g of adipic acid (73 mol%), 246 g of 1,4-butanediol (130 mol%) and 0.34 ml of glycerol (0.1% by weight based on the polymer) were mixed together with 0.37 ml of tetrabutyl orthotitanate (TBOT), the molar ratio between alcohol components and acid component being 1.30.
  • TBOT tetrabutyl orthotitanate
  • the reaction mixture was heated to a temperature of 210 ° C and held at this temperature for 2 hours. Subsequently, the temperature was raised to 240 ° C and gradually evacuated. The excess dihydroxy compound was distilled off under a vacuum of less than 1 mbar over a period of 3 h.
  • the polyester A1 thus obtained had a melting point of 60 ° C and a V
  • a polybutylene terephthalate adipate prepared as follows: 583.3 g of dimethyl terephthalate (27 mol%), 1280.2 g of adipic acid (73 mol%), 1405.9 g of 1,4-butanediol (130 mol%) and 37 g Glycerol (1, 5 wt .-% based on the polymer) were mixed together with 1 g of tetrabutyl orthotitanate (TBOT), wherein the molar ratio between alcohol components and acid component was 1.30.
  • TBOT tetrabutyl orthotitanate
  • polyester A3 had a melting point of 60 ° C and a VZ of 146 ml / g. Polyester A3
  • a polybutylene terephthalate adipate prepared as follows: 697.7 g of terephthalic acid (35 mol%), 1 139.9 g of adipic acid (65 mol%), 1405.9 g of 1,4-butanediol
  • polyester A3 had a melting point of 80 ° C (broad) and a VZ of 191 ml / g. Polyester A4
  • a polybutylene terephthalate adipate prepared as follows: 726.8 g of terephthalic acid (35 mol%), 1 187.4 g of adipic acid (65 mol%), 1464.5 g of 1,4-butanediol
  • the reaction mixture was heated to a temperature of 210 ° C and held at this temperature for 2 hours. Subsequently, the temperature was raised to 240 ° C and gradually evacuated. The excess dihydroxy compound was distilled off under a vacuum of less than 1 mbar over a period of 3 h.
  • the polyester A4 thus obtained had a melting point of 80 ° C and a VZ of 157 ml / g.
  • a polybutylene terephthalate adipate prepared as follows: 87.3 kg of dimethyl terephthalate (44 mol%), 80.3 kg of adipic acid (56 mol%), 17 g of 1, 4-butanediol and 0.2 kg of glycerol (0, 1% by weight based on the polymer) were mixed together with 0.028 kg of tetrabutyl orthotitanate (TBOT), the molar ratio between alcohol components and acid component being 1.30.
  • TBOT tetrabutyl orthotitanate
  • 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 ° C and the excess dihydroxy compound distilled off under vacuum over a period of 3h.
  • the polyester B1 thus obtained had a melting temperature of 1 19 ° C and a molecular weight (M n ) of 23000 g / mol, molecular weight (M w ) of 13000 g / mol.
  • polyesters A1, A3, A4 and Comparative Example B1 were hot presses to the press foils FA1; FA3, FA4 and comparative film FB1 processed and subjected to a hysteresis test.
  • the hysteresis test was carried out on 60 m thick films according to DIN 53835 at 23 ° C. First the slides were cut to 4mm * 25mm. Such film was then loaded at 120 mm / min. After reaching the 50% elongation, the film was relieved without holding time (first measurement of the resilience). Then it waited 6 minutes. This was followed by the second cycle with the 100% stretch in the top.
  • the films which consist of a polyester with a low terephthalic acid content such as, for example, FA1, had a higher restoring force than the comparison film FB1.
  • a further increase in the restoring force experienced films with a high crosslinking agent content (FA3 compared to FA4).

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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)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Laminated Bodies (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

La présente invention concerne un procédé de réalisation de films adhésifs, par utilisation de polyesters biodégradables qui peuvent être obtenus par polycondensation de : i) 65 à 80 % molaires, rapportés aux constituants i à ii, d'un ou de plusieurs dérivés d'acide dicarboxylique ou acides dicarboxyliques choisis dans le groupe comprenant l'acide succinique, l'acide adipique, l'acide sébacique, l'acide azélaïque et l'acide brassylique; ii) 35 à 20 % molaires, rapportés aux constituants i à ii, d'un dérivé d'acide téréphtalique; iii) 98 à 102 % molaires, rapportés aux constituants i à ii, d'un alkylènediol en C2-C8 ou d'un oxyalkylènediol en C2-C6; iv) 0,1 à 2 % en poids, rapportés au polymère obtenu à partir des constituants i à iii, d'un agent de réticulation au moins trifonctionnel ou d'un allongeur de chaîne au moins bifonctionnel. L'invention a également pour objet des mélanges polymères qui conviennent particulièrement pour la réalisation de films adhésifs et des films adhésifs qui contiennent des polyesters biodégradables.
PCT/EP2011/054386 2010-03-24 2011-03-23 Procédé de réalisation de films adhésifs WO2011117265A1 (fr)

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EP11709426A EP2550330A1 (fr) 2010-03-24 2011-03-23 Procédé de réalisation de films adhésifs
CA2792845A CA2792845A1 (fr) 2010-03-24 2011-03-23 Procede de realisation de films adhesifs
AU2011231669A AU2011231669A1 (en) 2010-03-24 2011-03-23 Process for producing cling films
CN2011800155350A CN102869723A (zh) 2010-03-24 2011-03-23 制备保鲜膜的方法
KR1020127027563A KR20130010080A (ko) 2010-03-24 2011-03-23 클링필름의 제조 방법

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CN104356372B (zh) * 2014-10-27 2016-10-26 清华大学 一种枝化脂肪-芳香族共聚酯及其合成方法
CN109401212B (zh) * 2017-08-16 2022-12-13 中国石油化工股份有限公司 聚酯组合物和热收缩薄膜及其制备方法
CN109401216B (zh) * 2017-08-16 2022-07-12 中国石油化工股份有限公司 聚酯组合物和功能层及其制备方法和应用
EP3530694A4 (fr) 2016-10-21 2020-06-10 China Petroleum&Chemical Corporation Composition de polyester, son procédé de préparation et son utilisation
CN109401211B (zh) * 2017-08-16 2022-12-13 中国石油化工股份有限公司 聚酯组合物和医用肢体固定支架及其制备方法
CN109401213B (zh) * 2017-08-16 2022-07-12 中国石油化工股份有限公司 聚酯组合物和3d打印线材及其制备方法
CN109401215B (zh) * 2017-08-16 2022-07-12 中国石油化工股份有限公司 聚酯组合物和无纺布及其制备方法和应用
CN109401214B (zh) * 2017-08-16 2022-06-21 中国石油化工股份有限公司 聚酯组合物和弹性纤维及其制备方法
IT202000015022A1 (it) 2020-06-23 2021-12-23 Novamont Spa Pellicole per l’imballaggio con agente antiappannante
KR102436243B1 (ko) * 2020-10-20 2022-08-26 주식회사 안코바이오플라스틱스 기계적 물성, 성형성 및 내후성이 향상된 자연유래 생분해성 수지 조성물 및 그 제조방법
CN114763429B (zh) * 2021-05-17 2024-01-26 瑞拓峰高新科技有限公司 一种具有高度相容性的生物降解聚酯合金的合成方法

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KR20130010080A (ko) 2013-01-25

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