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WO2004067632A1 - Polyesters biodegradables a comportement en traitement ameliore - Google Patents

Polyesters biodegradables a comportement en traitement ameliore Download PDF

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Publication number
WO2004067632A1
WO2004067632A1 PCT/EP2004/000458 EP2004000458W WO2004067632A1 WO 2004067632 A1 WO2004067632 A1 WO 2004067632A1 EP 2004000458 W EP2004000458 W EP 2004000458W WO 2004067632 A1 WO2004067632 A1 WO 2004067632A1
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Prior art keywords
acid
component
weight
polyesters
mixtures
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PCT/EP2004/000458
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German (de)
English (en)
Inventor
Motonori Yamamoto
Uwe Witt
Hans-Peter Vollmann
Gabriel Skupin
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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
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • 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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to thermoplastic molding compositions containing
  • ii) 0.01 to 10% by weight, based on the total weight of components i) to ii) of at least one polyester based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound and
  • iii) moreover 0 to 80% by weight, based on the weight of component i), of conventional additives.
  • the present invention relates to processes for the production of thermoplastic molding compositions, the use of thermoplastic molding compositions for the production of blends, moldings, films or fibers, blends, moldings, films or fibers containing thermoplastic molding compositions and the use of polyesters based on aromatic dicarboxylic acids and aliphatic or aromatic dihydroxy compounds as nucleating agents for polyesters which are biodegradable according to DIN V 54900.
  • Biodegradable polyesters are known.
  • EP-A 792309 describes partially aromatic polyesters which, in addition to having good mechanical properties, have good biodegradability.
  • Such biodegradable polyesters often tend to delay or slow crystallization when cooled from the melt, which can lead to disadvantages in the processing of the melts.
  • delayed or slow-crystallizing polyester melts tend to adhere to the film during processing, for example into films
  • nucleating agents for example talc
  • talc talc
  • the nucleating agents known to the person skilled in the art do not have a sufficient action in the biodegradable polyesters.
  • the present invention is therefore based on the object of providing thermoplastic molding compositions based on biodegradable polyesters which, compared to known molding compositions, have less delayed or accelerated crystallization when cooling from the melt, which have a reduced tendency to stick to the tools during processing, and which enable increased throughput during processing.
  • thermoplastic molding compositions defined at the outset which are described in more detail below.
  • polyesters that are biodegradable can be considered as component i) for the production of the thermoplastic molding compositions according to the invention.
  • biodegradable polyester is intended to include all polyesters that meet the definition of biodegradability given in DIN V 54900, in particular compostable polyesters.
  • biodegradability means that the polyesters disintegrate in a reasonable and detectable period of time.
  • the breakdown can take place hydrolytically and / or oxidatively and can be mainly caused by the action of microorganisms such as bacteria, yeasts, fungi and algae.
  • Biodegradability can be determined, for example, by mixing polyester with compost and storing it for a certain time. According to ASTM D 5338, ASTM D 6400, EN 13432 and DIN V 54900, C0 2 -free air is allowed to flow, for example, through matured compost during composting and this is subjected to a defined temperature program.
  • the biodegradability of the relationship of the net-C0 2 release of the sample is subjected to a defined temperature program.
  • Biodegradable polyesters usually show clear signs of degradation such as fungal growth, cracking and pitting after just a few days of composting.
  • biodegradable polyesters examples include cellulose derivatives such as cellulose esters, e.g. Cellulose acetate, cellulose acetate butyrate, starch esters, and polyester, in particular aliphatic homo- and copolyesters and partially aromatic copolyesters. Mixtures or blends of the aforementioned biodegradable polyesters are of course also suitable.
  • the biodegradable polyesters i) mentioned can contain, as blend or blend components, other biodegradable polymers of natural or synthetic origin.
  • Polymers of natural origin are, for example, shellac, starch or cellulose. These can be modified with physical and / or chemical methods.
  • the preferred polymers of natural origin include starch, thermoplastically processable starch or Starch compounds such as starch ether.
  • the weight ratio of biodegradable polyesters i) to other biodegradable blend or blend components, for example starch can be chosen freely in a wide range, for example in the range from 1.2: 1 to 0.8: 1.2.
  • Polymeric reaction products of lactic acid can be used as biodegradable polyesters i) for the production of the thermoplastic molding compositions according to the invention. These are known per se or can be produced by processes known per se.
  • copolymers or block copolymers based on lactic acid and other monomers can also be used. Linear polylactides are mostly used. However, branched lactic acid polymers can also be used. For example, multifunctional acids or alcohols can serve as branching agents.
  • Examples include polylactides which essentially consist of lactic acid or its d- to C 4 -alkyl esters or mixtures thereof and at least one aliphatic C 4 - to C 10 -dicarboxylic acid and at least one C 3 - to G- 0 alkanol with three to five Hydroxy groups are available.
  • biodegradable polyesters i) from which the thermoplastic molding compositions according to the invention can be obtained are, moreover, aliphatic polyesters. These include homopolymers of aliphatic hydroxycarboxylic acids or lactones but also copolymers or block copolymers of different hydroxycarboxylic acids or lactones or mixtures thereof. These aliphatic polyesters can also contain diols and / or isocyanates as building blocks. In addition, the aliphatic polyesters can also contain building blocks which are derived from trifunctional or multifunctional compounds such as epoxides, acids or triols. The latter building blocks can be contained individually or several of them or together with the diols and / or isocyanates in the aliphatic polyesters.
  • the aliphatic polyesters generally have molecular weights M n in the range from 1,000 to 100,000 g / mol.
  • Polycaprolactone is one of the particularly preferred aliphatic polyesters.
  • Poly-3-hydroxybutanoic acid esters and copolymers of 3-hydroxybutanoic acid or their mixtures with 4-hydroxybutanoic acid and 3-hydroxyvaleric acid, in particular up to 30, preferably up to 20% by weight of the latter acid, are particularly preferred aliphatic polyesters .
  • Suitable polymers of this type also include those with an R-stereospecific configuration, as are known from WO 96/09402.
  • Polyhydroxybutanoic acid esters or their copolymers can be produced microbially. Processes for the production from different bacteria and fungi are for example the message Chem Tech. Lab. 39, 1112-1124 (1991), a method for producing stereospecific polymers is known from WO 96/09402.
  • block copolymers of the hydroxycarboxylic acids or lactones mentioned, their mixtures, oligomers or polymers can also be used.
  • aliphatic polyesters are those which are composed of aliphatic or cycloaliphatic dicarboxylic acids or their mixtures and aliphatic or cycloaliphatic diols or their mixtures. According to the invention, both statistical and block copolymers can be used.
  • the aliphatic dicarboxylic acids suitable according to the invention generally have 2 to 10 carbon atoms, preferably 4 to 6 carbon atoms. 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 having 8 carbon atoms. In principle, however, dicarboxylic acids with a larger number of carbon atoms, for example with up to 30 carbon atoms, can also be used.
  • Examples include: malonic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, acelic 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 and 2,5-norbornanedicarboxylic acid, among which adipic acid is preferred.
  • ester-forming derivatives of the above-mentioned aliphatic or cycloaliphatic dicarboxylic acids are in particular the di-Cr to C 6 -alkyl esters, such as dimethyl, diethyl, di-n-propyl, di-isopropyl, di-n -butyl, di-iso-butyl, di-t-butyl, di-n-pentyl, di-iso-pentyl or di-n-hexyl esters.
  • Anhydrides of the dicarboxylic acids can also be used.
  • the dicarboxylic acids or their ester-forming derivatives can be used individually or as a mixture of two or more thereof.
  • Suitable aliphatic polyesters are aliphatic copolyesters as described in WO 94/14870, in particular aliphatic copolyesters from succinic acid, its diesters or their mixtures with other aliphatic acids or Diesters such as glutaric acid and butanediol or mixtures of this diol with ethylene glycol, propanediol or hexanediol or mixtures thereof.
  • Aliphatic polyesters of this type generally have molecular weights M n in the range from 1000 to 100000 g / mol.
  • the aliphatic polyesters can likewise be random or block copolyesters which contain further monomers.
  • the proportion of the other monomers is usually up to 10% by weight.
  • Preferred comonomers are hydroxycarboxylic acids or lactones or mixtures thereof.
  • Mixtures of two or more comonomers and / or further building blocks, such as epoxides or polyfunctional aliphatic or aromatic acids or polyfunctional alcohols, can of course also be used to prepare the aliphatic polyesters.
  • thermoplastic molding compositions according to the invention can be based on partially aromatic polyesters as component i). According to the invention, this should also include polyester derivatives such as polyether esters, polyester amides or polyether ester amides. Suitable biodegradable partially aromatic polyesters include linear non-chain extended polyesters (WO 92/09654). Chain-extended and / or branched partially aromatic polyesters are preferred. The latter are known from the documents mentioned at the beginning, 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, as are blends of partially aromatic polyesters with starch or modified starch, cellulose esters or polylactide.
  • the particularly preferred partially aromatic polyesters include polyesters, which are essential components
  • a diol component selected from at least one C 2 to C ⁇ 2 alkanediol and at least one C 5 - to C ⁇ 0 -Cycloalkandiol or mixtures thereof
  • n 2, 3 or 4 and m is an integer from 2 to 250
  • At least one aminocarboxylic acid selected from the group consisting of the natural amino acids, polyamides with a molecular weight of at most 18000 g / mol, obtainable by polycondensation of a dicarboxylic acid with 4 to 6 C atoms and a diamine with 4 to 10 C atoms, compounds of the formulas IV a and IVb
  • T is a radical which is selected from the group consisting of phenylene, - (CH 2 ) U -, where u is an integer from 1 to 12, -C (R) H- and - C (R 2 ) HCH 2 , where R 2 is methyl or ethyl,
  • R 3 represents hydrogen, C 1 -C 6 -alkyl, C 5 -C 8 cycloalkyl, unsubstituted or with C 1 -C 4 -alkyl groups up to triply substituted phenyl or tetrahydrofuryl,
  • the acid component A of the partially aromatic polyesters preferably contains from 30 to 70, in particular from 40 to 60 mol% a1 and from 30 to 70, in particular from 40 to 60 mol% a2.
  • the aliphatic or cycloaliphatic acids and the corresponding derivatives a1 are those mentioned above.
  • Adipic acid or sebacic acid or their respective ester-forming derivatives or mixtures thereof are particularly preferably used.
  • Adipic acid or its ester-forming derivatives, such as its alkyl esters or mixtures thereof, are particularly preferably used.
  • Aromatic dicarboxylic acid a2 is generally those with 8 to 12 carbon atoms and preferably those with 8 carbon atoms. Examples include terephthalic acid, isophthalic acid, 2,6-naphthoic acid and 1, 5-naphthoic acid and ester-forming derivatives thereof.
  • the di-CrC ⁇ alkyl esters e.g. Dimethyl, diethyl, di-n-propyl, di-iso-propyl, di-n-butyl, di-iso-butyl, di-t-butyl, di-n-pentyl, di-iso-pentyl or to name di-n-hexyl ester.
  • the anhydrides of dicarboxylic acids a2 are also suitable ester-forming derivatives.
  • aromatic dicarboxylic acids a2 with a larger number of carbon atoms, for example up to 20 carbon atoms, can also be used.
  • aromatic dicarboxylic acids or their ester-forming derivatives a2 can be used individually or as a mixture of two or more thereof.
  • Terephthalic acid or its ester-forming derivatives such as dimethyl terephthalate are particularly preferably used.
  • the sulfonate group-containing compound used is usually an alkali metal or alkaline earth metal salt of a sulfonate group-containing dicarboxylic acid or its ester-forming derivatives, preferably alkali metal salts of 5-sulphoisophthalic acid or mixtures thereof, particularly preferably the sodium salt.
  • the acid component A contains from 40 to 60 mol% a1, from 40 to 60 mol% a2 and from 0 to 2 mol% a3.
  • the acid component A contains from 40 to 59.9 mol% a1, from 40 to 59.9 mol% a2 and from 0.1 to 1 mol% a3, in particular from 40 to 59.8 mol -% a1, from 40 to 59.8 mol% a2 and from 0.2 to 0.5 mol% a3.
  • the diols B are selected from branched or linear alkane diols having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, or cycloalkane diols 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,
  • the moi ratio of the components A to B used can be in the range from 0.4: 1 to 1.5: 1, preferably in the range from 0.6: 1 to 1.1: 1.
  • the polyesters on which the molding compositions according to the invention are based can contain further components.
  • poly-THF polytetrahydrofuran
  • the molecular weight (M n ) of the polyethylene glycol is generally chosen in the range from 250 to 8000, preferably from 600 to 3000 g / mol. According to one of the preferred embodiments, for example from 15 to 98, preferably 60 to 99.5 mol% of the diols B and 0.2 to 85, preferably 0.5 to 30 mol% of the dihydroxy compounds d, based on the molar Amount of B and d used for the production of the partially aromatic polyester.
  • the hydroxycarboxylic acid c2) used is: glycolic acid, D-, L-, D, L-lactic acid, 6-hydroxyhexanoic acid, its cyclic derivatives such as glycolide (1,4-dioxane-2,5-dione), D -, L-dilactide (3,6-dimethyl-1, 4-dioxane-2,5-dione), p-hydroxybenzoic acid as well as their oligomers and polymers such as 3-polyhydroxybutyric acid, polyhydroxyvaleric acid, polylactide (for example, as EcoPLA ® (from Cargill.
  • EcoPLA ® from Cargill.
  • the hydroxycarboxylic acids can be used, for example, in amounts of from 0.01 to 50, preferably from 0.1 to 40,% by weight, based on the amount of A and B.
  • Amino-C 2 -C 2 -alkanol or amino-C 5 -C- 0 -cyloalkanol (component c3), which should also include 4-aminomethylcyclohexane-methanol, are preferably amino-C 2 -C 6 -alkanols such as 2-aminoethanol , 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol and amino-C 5 -C 6 -cycloalkanols such as aminocyclopentanol and aminocyclohexanol or mixtures thereof.
  • the diamino-CrC- 8- alkane (component c4) is preferably a diamino-C-C 6 -alkane such as 1,4-diminobutane, 1,5-diaminopentane and 1,6-diaminohexane (hexamethylenediamine, "HMD").
  • from 0.5 to 99.5 mol%, preferably 0.5 to 50 mol%, c3, based on the molar amount of B, and from 0 to 50, preferably from 0 to 35 mol% , c4, based on the molar amount of B, can be used for the production of the partially aromatic polyesters.
  • the 2,2'-bisoxa ⁇ olines c5 of the general formula III are generally obtainable by the process from Angew. Chem. Int. Edit, Vol. 11 (1972), pp. 287-288.
  • bisoxazolines are 2,2'-bis (2-oxazoline), bis (2-oxazolinyl) methane, 1,2-bis (2-oxazolinyl) ethane, 1,3-bis (2-oxazolinyl) propane or 1 , 4-bis (2-oxazolinyl) butane, in particular 1, 4-bis (2-oxazolinyl) benzene, 1, 2-bis (2-oxazolinyl) benzene or 1, 3-bis (2-oxazolinyl) benzene called.
  • the partially aromatic polyesters for example from 70 to 98 mol% of B, up to 30 mol% of c3 and 0.5 to 30 mol% of c4 and 0.5 to 30 mol% of c5, in each case based on the sum of the molar amounts of components B, c3, c4 and c5 can be used. According to another preferred embodiment, it is possible to use from 0.1 to 5, preferably 0.2 to 4% by weight of c5, based on the total weight of A and B.
  • Natural aminocarboxylic acids can be used as component c6. These include valine, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, lysine, alanine, arginine, aspartic acid, cysteine, glutamic acid, glycine, histidine, proline, serine, tryosine, asparagine or glutamine.
  • Preferred aminocarboxylic acids of the general formulas IVa and IVb are those in which s is an integer from 1 to 1000 and t is an integer from 1 to 4, preferably 1 or 2 and T is selected from the group consisting of phenylene and - (CH 2 ) U -, where u is 1, 5 or 12.
  • c6 can also be a polyoxazoline of the general formula V.
  • C6 can also be a mixture of different aminocarboxylic acids and / or polyoxazolines.
  • c6 can be used in amounts of from 0.01 to 50, preferably from 0.1 to 40,% by weight, based on the total amount of components A and B.
  • Compounds d1 which contain at least three groups capable of ester formation are further components which can optionally be used for the production of the partially aromatic polyesters.
  • the compounds d1 preferably contain three to ten functional groups which are capable of forming ester bonds. Particularly preferred compounds d1 have three to six functional groups of this type in the molecule, in particular three to six hydroxyl groups and / or carboxyl groups. Examples include:
  • Tartaric acid citric acid, malic acid; Trimethylolpropane, trimethylolethane; pentaerythritol; polyether triols; glycerol; trimesic; Trimellitic acid, anhydride; Pyromellitic acid, dianhydride and hydroxyisophthalic acid.
  • the compounds d1 are generally used in amounts of 0.01 to 15, preferably 0.05 to 10, particularly preferably 0.1 to 4 mol%, based on component A.
  • Aromatic or aliphatic diisocyanates can be used. However, higher functional isocyanates can also be used.
  • 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate are particularly preferred as component d2.
  • the latter diisocyanates are generally used as a mixture.
  • Tri (4-isocyanophenyl) methane can also be used as the trinuclear isocyanate d2.
  • the multinuclear aromatic diisocyanates are obtained, for example, in the production of mononuclear or dinuclear diisocyanates.
  • component d2 can also contain urethione groups, for example for capping the isocyanate groups.
  • an aliphatic diisocyanate d2 is primarily linear or branched alkylene diisocyanate or cycloalkylene diisocyanate having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, for example 1,6-hexamethylene diisocyanate, isophorone diisocyanate or methylene bis (4-isocyanatocyclohexane), Roger that.
  • Particularly preferred aliphatic diisocyanates d2 are 1,6-hexamethylene diisocyanate and isophorone diisocyanate.
  • the preferred isocyanurates include the aliphatic isocyanurates which are derived from alkylene diisocyanates or cycloalkylene diisocyanates having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, for example isophorone diisocyanate or methylene bis (4-isocyanatocyclohexane).
  • the alkylene diisocyanates can be linear or branched. Isocyanurates based on n-hexamethylene diisocyanate, for example cyclic trimers, pentamers or higher oligomers of n-hexamethylene diisocyanate, are particularly preferred.
  • component d2 is used in amounts of 0.01 to 5, preferably 0.05 to 4 mol%, particularly preferably 0.1 to 4 mol%, based on the sum of the molar amounts of A and B.
  • divinyl ether d3 all customary and commercially available divinyl ethers can be used as the divinyl ether d3.
  • 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether or 1,4-cyclohexanedimethanol divinyl ether or mixtures thereof are preferably used.
  • the divinyl ethers are preferably used in amounts of from 0.01 to 5, in particular from 0.2 to 4,% by weight, based on the total weight of A and B.
  • Examples of preferred partially aromatic polyesters are based on the following components
  • partially aromatic polyesters based on A, B, d1 or A, B, d2 or on A, B, d1, d2 are particularly preferred.
  • the partially aromatic polyesters are based on A, B, c3, c4, c5 or A, B, d1, c3, c5.
  • the production of the partially aromatic polyesters is known per se or can be carried out according to methods known per se.
  • the preferred partially aromatic polyesters are characterized by a molecular weight (M ⁇ ) in the range from 1000 to 100000, in particular in the range from 9000 to 75000 g / mol, preferably in the range from 10000 to 50,000 g / mol and a melting point in the range from 60 to 170 , preferably in the range from 80 to 150 ° C.
  • M ⁇ molecular weight
  • the aliphatic and / or partially aromatic polyesters mentioned can have hydroxyl and / or carboxyl end groups in any ratio.
  • the aliphatic and / or partially aromatic polyesters mentioned 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.
  • components ii) of the thermoplastic molding compositions are polyesters based on aromatic dicarboxylic acids and aliphatic or aromatic dihydroxy compounds. These polyesters suitable as component ii) are not biodegradable because of their high proportion of aromatic units.
  • a first group of preferred polyesters ii) are polyalkylene terephthalates, in particular with 2 to 10 carbon atoms in the alcohol part.
  • Such polyalkylene terephthalates are known per se and are described in the literature. They contain an aromatic ring in the main chain, which comes from the aromatic dicarboxylic acid.
  • the aromatic ring can also be substituted, e.g. by halogen such as chlorine and bromine or by d-Cr-alkyl groups such as methyl, ethyl, i- or n-propyl and n-, i- or t-butyl groups.
  • polyalkylene terephthalates can be prepared in a manner known per se by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds.
  • Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof.
  • Up to 20 mol%, preferably not more than 10 mol%, of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and Cyclohexanedicarboxylic acids are replaced.
  • diols having 2 to 6 carbon atoms in particular 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol, 1 , 4-Cyclohexanedimethanol and neopentyl glycol or mixtures thereof are preferred.
  • polyesters ii) are polyalkylene terephthalates which are derived from alkanediols having 2 to 6 carbon atoms. Of these, primarily polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof, in particular polybutylene terephthalate, are preferred. Also preferred are PET and / or PBT, which can also contain up to 1% by weight of 1,6-hexanediol and / or 2-methyl-1,5-pentanediol as further monomer units.
  • the viscosity number of the polyesters suitable as component ii) is generally in the range from 50 to 220 ml / g, preferably from 80 to 160 ml / g (measured in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture (Weight ratio 1: 1 at 25 ° C) according to EN ISO 1628-1.
  • PET recyclates also called scrap PET
  • PBT polyalkylene terephthalates
  • So-called post industrial recyclate this is production waste from polycondensation or processing e.g. Sprues in injection molding processing, approach goods in injection molding processing or extrusion or edge sections of extruded sheets or foils.
  • Post consumer recyclate these are plastic articles that are collected and processed by the end consumer after use.
  • the most dominant item in terms of quantity are blow-molded PET bottles for mineral water, soft drinks and juices.
  • Both types of recyclate can either be in the form of regrind or in the form of granules. In the latter case, the pipe cyclates are melted and granulated in an extruder after separation and cleaning. This usually means handling, free-flowing and ease of metering for further processing steps.
  • Recyclates both granulated and in the form of regrind, can be used, the maximum edge length being 6 mm, preferably less than 5 mm.
  • the residual moisture content after drying is preferably ⁇ 0.2%, in particular ⁇ 0.05%.
  • Another group of the compounds suitable as component Ii) are fully aromatic polyesters which are derived from aromatic dicarboxylic acids and aromatic dihydroxy compounds.
  • Aromatic dicarboxylic acids which are suitable are the compounds already described for the polyalkylene terephthalates. Mixtures of 5 to 100 mol% of isophthalic acid and 0 to 95 mol% of terephthalic acid, in particular mixtures of approximately 80% terephthalic acid with 20% isophthalic acid to approximately equivalent mixtures of these two acids, are preferably used for fully aromatic polyester.
  • the aromatic dihydroxy compounds preferably have the general formula (VI)
  • Z represents an alkylene or cycloalkylene group with up to 8 C atoms, an arylene group with up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in the m 'the value 0 has up to 2.
  • the compounds can also carry G 1 -C 6 -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene groups.
  • polyalkylene terephthalates and fully aromatic polyesters as component ii). These generally contain 20 to 98% by weight. % of the polyalkylene terephthalate and 2 to 80 wt .-% of the fully aromatic polyester.
  • polyester block copolymers such as copolyether esters can also be used as component ii).
  • Products of this type are known per se and are described in the literature, for example in US Pat. No. 3,651,014.
  • Corresponding products are also commercially available, for example Hytrel ® (DuPont).
  • polyester ii) should also be understood to mean polycarbonates. Suitable polycarbonates are, for example, those based on diphenols of the general formula (VII)
  • Q is a single bond, a d to C 8 alkylene, a C 2 to C 3 alkylidene, a Gabis C 6 cycloalkylidene group, a C 6 to C 2 arylene group and -O-, -S- or -S0 2 - means and n 'is an integer from 0 to 2.
  • the diphenols may also have substituents such as d- to C 6
  • Preferred diphenols of the formula VII are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1, 1-bis (4-hydroxyphenyl) -cyclohexane.
  • 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3,5- are particularly preferred. trimethylcyclohexane.
  • both homopolycarbonates and copolycarbonates are suitable as component ii); in addition to the bisphenol A homopolymer, the copolycarbonates of bisphenol A are preferred.
  • the suitable polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of at least trifunctional compounds, for example those having three or more than three phenolic compounds OH groups.
  • have from 1, 10 to 1, 50, in particular from 1, 25 to 1, 40. This corresponds to average molecular weights M w (weight average) of 10,000 to 200,000, preferably from 20,000 to 80,000 g / mol.
  • the diphenols of the general formula VII are known per se or can be prepared by known processes.
  • the polycarbonates can be prepared, for example, by reacting the diphenols with phosgene by the interfacial process or with phosgene by the process in a homogeneous phase (the so-called pyridine process), the molecular weight to be set in each case being achieved in a known manner by a corresponding amount of known chain terminators. (Regarding polycarbonates containing polyidiorganosiloxane, see for example DE-OS 3334782).
  • Suitable chain terminators are, for example, phenol, pt-butylphenol but also long-chain alkylphenols such as 4- (1,3-tetramethylbutyl) phenol, according to DE-OS 28 42 005 or monoalkylphenols or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents according to DE-A 35 06472, such as p-nonylphenyl, 3,5-di-t-butylphenol, pt-octylphenol, p-dodecylphenol, 2- (3,5-dimethyl-heptyl) -phenol and 4- (3rd , 5-dimethylheptyl) -phenol.
  • alkylphenols such as 4- (1,3-tetramethylbutyl) phenol, according to DE-OS 28 42 005 or monoalkylphenols or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents according
  • Amorphous polyester carbonates may be mentioned as further suitable components ii), with phosgene being replaced by aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units during production.
  • aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units during production.
  • Bisphenol A can also be replaced by Bisphenol TMC.
  • Such polycarbonates are available under the trademark APEC HT ® from Bayer AG.
  • thermoplastic molding compositions according to the invention usually contain from 90 to 99.99% by weight, preferably from 95 to 99.95% by weight, particularly preferably from 99 to 99.9% by weight of component i) and from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 1% by weight, of component ii), the percentages by weight in each case relating to the total weight of components i) to ii) ,
  • thermoplastic molding compositions and / or the polyesters i) can contain additives iii) which can be incorporated during the polymerization process in any stage or subsequently, for example into a melt of the polyester, or together with the incorporation of component ii).
  • additives iii) which can be incorporated during the polymerization process in any stage or subsequently, for example into a melt of the polyester, or together with the incorporation of component ii).
  • Stabilizers, neutralizing agents, lubricants and release agents, antiblocking agents, dyes or fillers are mentioned as examples.
  • additives Based on the polyester i), from 0 to 80% by weight of additives can be added. Suitable additives are, for example, fillers, stabilizers or lubricants and mold release agents. Sol- Before additives are described in detail, for example, in Kunststoff-Handbuch, Vol. 3/1, Carl Hanser Verlag, Kunststoff, 1992, pp. 24 to 28.
  • fillers are particulate substances such as calcium carbonate, clay minerals, calcium sulfate, barium sulfate, titanium dioxide, carbon black, lignin powder, iron oxide, which can also act as color-imparting components, and fiber materials, e.g. Cellulose fibers, sisal and hemp fibers.
  • the proportion of fillers is generally not more than 40% by weight, based on the total weight of the molding composition according to the invention, in particular not more than 20% by weight.
  • Stabilizers are e.g. Tocopherol (vitamin E), organic phosphorus compounds, mono-, di- and polyphenols, hydroquinones, diarylamines, thioethers, melamine or urea.
  • anti-blocking agents come e.g. Talc, chalk, mica or silicon oxides into consideration.
  • Lubricants and mold release agents are generally substances based on 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, e.g. Paraffin waxes, beeswax, montan waxes and the like.
  • Preferred release agents are erucic acid amide and / or wax types and particularly preferably combinations of these two types of release agents.
  • Preferred wax types are beeswaxes and ester waxes, in particular glycerol monostearate.
  • the polyesters i) used to produce the molding compositions according to the invention are particularly preferably equipped with 0.05 to 2.0% by weight erucic acid amide or 0.1 to 2.0% by weight wax types, in each case based on the plastic content of the molding compositions.
  • polyesters i) used to produce the molding compositions according to the invention with 0.05 to 0.5% by weight erucic acid amide and 0.1 to 1.0% by weight wax types, in particular glycerol monostearate, are in each case based on the plastic content of the Molding compounds, equipped.
  • the polyesters which can be used according to the invention as component ii) can be introduced into the polyesters i) to be stabilized by various methods.
  • the polyesters ii) can be combined with one or more of the monomer components for the preparation of the polyesters i), e.g. the dicarboxylic acids and / or diols can be admixed during the preparation of component i).
  • the polyesters ii) can be incorporated into the melt of the fully reacted polyesters i).
  • Component ii) can be introduced into the previously prepared polyester i) using known processes and with the aid of known mixing devices (see, for example, Saechling, Kunststoff-Taschenbuch, Hanser Verlag, Kunststoff, Vienna, edition 26, 1995, pages 191 to) 246).
  • Component ii) can, for example with the help of a screw machine, for example an extruder, either in pure form or as a so-called "masterbatch", in component i) to be mixed in.
  • these masterbatches are special molding compositions in which the required additives or additives, for example component ii), are embedded in a matrix of, for example, thermoplastic polymer, for example component i), but the additive content compared to conventional ones additive molding compositions is significantly higher, for example in the range from 10 to 70% by weight.
  • a masterbatch to, for example, a non-additive thermoplastic, molding compositions can then be produced with the usual additive contents.
  • thermoplastic molding compositions according to the invention are particularly suitable for the production of blends, moldings, films or fibers.
  • Blends with polysaccharides or polysaccharin derivatives, in particular starch, can particularly preferably be produced from the molding compositions according to the invention, which in turn can be processed into films, moldings or fibers.
  • a particular field of application of the molding compositions according to the invention relates to their use as a compostable film or a compostable coating, for example as a mulch film.
  • thermoplastic molding compositions according to the invention relates to the production of completely degradable blends with starch mixtures (preferably with thermoplastic starch as described in WO 90/05161) analogously to the process described in DE-A 4237535.
  • the molding compositions according to the invention can be mixed both as granules and as a polymer melt with starch mixtures, mixing being preferred as a polymer melt, since one process step (granulation) can be saved (direct assembly).
  • the thermoplastic molding compositions according to the invention can advantageously be used as a synthetic blend component on account of their hydrophobic nature, their mechanical properties, their biodegradability, their good compatibility with thermoplastic starch and not least because of their cheap raw material base.
  • molding compositions according to the invention relate, for example, to the use of the molding compositions according to the invention in agricultural mulch, packaging material for seeds and nutrients, substrate in adhesive films, baby panties, bags, bed sheets, bottles, boxes, dust bags, labels, pillow cases, protective clothing, hygiene articles, handkerchiefs, toys and wipers.
  • a further use of the molding compositions according to the invention relates to the production of foams, the procedure generally being known (see EP-A 372,846; Handbook of Polymeric foams and Foam Technology, Hanser Publisher, Kunststoff, 1991, pp. 375 to 408) , Usually, the molding composition according to the invention is first melted, then mixed with a blowing agent and the mixture thus obtained is subjected to reduced pressure by extrusion, the foaming being produced.
  • thermoplastic molding compositions With the help of the thermoplastic molding compositions according to the invention, biodegradable polyesters are provided which, compared to already known thermoplastic molding compositions based on biodegradable polyesters, have a less delayed or accelerated crystallization when cooling from the melt, which show a reduced tendency to stick to the tools during processing, and the one enable increased throughput during processing.
  • the molecular weight M n of the polymers was determined as follows: 15 mg of the polymers were dissolved in 10 ml of hexafluoroisopropanol (HFIP). In each case 125 ⁇ l of this solution were analyzed by means of gel permeation chromatography (GPC). The measurements were carried out at room temperature. HFIP + 0.05% by weight trifluoroacetic acid Ka salt was used for the elution. The elution rate was 0.5 ml / min.
  • the melting and crystallization temperatures of the molding compositions were determined by DSC measurements using an Exstet DSC 6200R from Seiko:
  • the polyester Pi-1 thus obtained had a melting temperature of 119 ° C. and a molecular weight (M n ) of 23,000 g / mol.
  • P-ii-1 Polybutylene terephthalate (PBT) with a viscosity number of 107 ml / g (VZ measured in
  • P-iii-1 erucic acid amide, commercial product from Sigma-Aldrich Chemie GmbH
  • P-iii-2 talcum powder ⁇ 10 ⁇ , commercial product from Sigma-Aldrich Chemie GmbH
  • the starting materials listed in Table 1 were mixed in a twin-screw extruder (ZSK30) at 230 ° C.
  • the melting and crystallization temperatures of the molding compositions thus obtained are also shown in Table 1.
  • the examples demonstrate the less delayed or accelerated crystallization of the molding compositions F-3 and F-5 compared to the molding composition F-V1 when cooling from the melt.
  • the starting materials specified in Table 2 were mixed in a twin-screw extruder (ZSK30) at 230 ° C. and granulated.
  • the molding compounds were then processed into films as follows: on a chill-roll system from Reifen Reifenberger with an extruder diameter of 90 mm, an extruder length of 2250 mm and two ghill-roll rollers (diameter of the first roller: 400 mm; diameter the second roller 150 mm) were from the molding compositions at a melt temperature of 175 ° C, a throughput of 38 kg / h, a drawing speed of 15 m / min, at the roller temperature given in Table 2 of both Ghill-Roll rollers and under otherwise the same conditions are produced using the chill-roll extrusion process.
  • Table 2 also shows the frequency with which the molding compositions were stuck to the chill-roll rollers during film production.
  • the sticking can be recognized by the fact that the film initially adheres to the first rotating roller beyond the normal detachment point and then detaches abruptly (in contrast, a non-sticking film detaches from the first rotating roller without jerking at the always the same detaching point) ).
  • the frequency of sticking shown in Table 2 is Number of visually detectable jerky detachment processes of the film from the first rotating roller per minute.
  • the films produced from the molding compositions F-1 to F-4 had a reduced tendency to stick to the tools during processing and enabled an increased throughput during processing than the films produced from the molding compositions F-V1 to F-V3.
  • the films produced from the molding compositions F-1 to F-4 had better transparency than the films produced from the molding compositions F-V1 to F-V3.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne des matières de moulage thermoplastiques contenant : i) entre 90 et 99,99 % en poids, par rapport au poids global des constituants i) à ii), d'au moins un polyester, biodégradable selon DIN V 54900, et ii) entre 0,01 et 10 % en poids, par rapport au poids global des constituants i) à ii) d'au moins un polyester à base d'acides dicarboxyliques aromatiques et d'un composé dihydroxy aliphatique ou aromatique et iii) en outre entre 0 et 80 % en poids, par rapport au poids du constituant i), d'additifs classiques. L'invention concerne en outre des procédés de production de matières de moulage thermoplastiques, l'utilisation de matières de moulage thermoplastiques pour produire des mélanges, des pièces moulées, des films ou des fibres, ainsi que les mélanges, les pièces moulées, les films ou les fibres contenant des matières de moulage thermoplastiques, ainsi que l'utilisation de polyesters à base d'acides dicarboxyliques aromatiques et de composés dihydroxy aliphatiques ou aromatiques, comme agents de nucléation pour polyesters, qui sont biodégradables selon DIN V 54900.
PCT/EP2004/000458 2003-01-27 2004-01-21 Polyesters biodegradables a comportement en traitement ameliore Ceased WO2004067632A1 (fr)

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DE2003103171 DE10303171A1 (de) 2003-01-27 2003-01-27 Biologisch abbaubare Polyester mit verbessertem Verarbeitungsverhalten
DE10303171.5 2003-01-27

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WO2007074042A3 (fr) * 2005-12-22 2007-12-06 Basf Ag Formulations d'agents de traitement de semences biodegradables
DE102007026719A1 (de) 2007-06-06 2008-12-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Biologisch abbaubare polymere Zusammensetzung aus natürlichen oder synthetischen Polymeren, Polyethylenoxid sowie ggf. Hilfs- und Zusatzstoffen ihre Herstellung, Weiterverarbeitung und Verwendung und hieraus hergestellte Erzeugnisse, vorzugsweise Folien
WO2011117308A1 (fr) 2010-03-24 2011-09-29 Basf Se Procédé de production de dispersions aqueuses de polyesters thermoplastiques
WO2013041649A1 (fr) 2011-09-23 2013-03-28 Basf Se Utilisation d'une dispersion aqueuse de polyesters biodégradables
US8604101B2 (en) 2010-03-24 2013-12-10 Basf Se Process for producing aqueous dispersions of thermoplastic polyesters

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Publication number Priority date Publication date Assignee Title
WO2015150141A1 (fr) * 2014-04-02 2015-10-08 Basf Se Mélange de polyesters

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WO1996015173A1 (fr) * 1994-11-15 1996-05-23 Basf Aktiengesellschaft Polymeres biodegradables, leur procede de production et leur utilisation pour la fabrication de corps moules biodegradables
EP1090958A2 (fr) * 1999-10-05 2001-04-11 Nippon Shokubai Co., Ltd. Composition de résine de polyester biodégradable et son utilisation
WO2002022736A1 (fr) * 2000-09-18 2002-03-21 Basf Aktiengesellschaft Film polyester
WO2003095555A1 (fr) * 2002-05-13 2003-11-20 E. I. Du Pont De Nemours And Company Compositions faites d'un melange de polyester et films biodegradables obtenus a partir de celles-ci

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WO1996015173A1 (fr) * 1994-11-15 1996-05-23 Basf Aktiengesellschaft Polymeres biodegradables, leur procede de production et leur utilisation pour la fabrication de corps moules biodegradables
EP1090958A2 (fr) * 1999-10-05 2001-04-11 Nippon Shokubai Co., Ltd. Composition de résine de polyester biodégradable et son utilisation
WO2002022736A1 (fr) * 2000-09-18 2002-03-21 Basf Aktiengesellschaft Film polyester
WO2003095555A1 (fr) * 2002-05-13 2003-11-20 E. I. Du Pont De Nemours And Company Compositions faites d'un melange de polyester et films biodegradables obtenus a partir de celles-ci

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007074042A3 (fr) * 2005-12-22 2007-12-06 Basf Ag Formulations d'agents de traitement de semences biodegradables
DE102007026719A1 (de) 2007-06-06 2008-12-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Biologisch abbaubare polymere Zusammensetzung aus natürlichen oder synthetischen Polymeren, Polyethylenoxid sowie ggf. Hilfs- und Zusatzstoffen ihre Herstellung, Weiterverarbeitung und Verwendung und hieraus hergestellte Erzeugnisse, vorzugsweise Folien
WO2011117308A1 (fr) 2010-03-24 2011-09-29 Basf Se Procédé de production de dispersions aqueuses de polyesters thermoplastiques
US8604101B2 (en) 2010-03-24 2013-12-10 Basf Se Process for producing aqueous dispersions of thermoplastic polyesters
WO2013041649A1 (fr) 2011-09-23 2013-03-28 Basf Se Utilisation d'une dispersion aqueuse de polyesters biodégradables

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