EP2688956A1 - Polyester à base d'acide 2-méthylsuccinique - Google Patents

Polyester à base d'acide 2-méthylsuccinique

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Publication number
EP2688956A1
EP2688956A1 EP12710701.9A EP12710701A EP2688956A1 EP 2688956 A1 EP2688956 A1 EP 2688956A1 EP 12710701 A EP12710701 A EP 12710701A EP 2688956 A1 EP2688956 A1 EP 2688956A1
Authority
EP
European Patent Office
Prior art keywords
component
acid
ester
forming derivative
mol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12710701.9A
Other languages
German (de)
English (en)
Inventor
Robert Loos
Darijo Mijolovic
Jens Heimann
Zsolt-Jozsef SZARKA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP12710701.9A priority Critical patent/EP2688956A1/fr
Publication of EP2688956A1 publication Critical patent/EP2688956A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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

Definitions

  • the present invention relates to a polyester containing repeating units based on at least one aliphatic dicarboxylic acid or an ester-forming derivative thereof (component A1), at least one aromatic dicarboxylic acid or an ester-forming derivative thereof (component A2), at least one diol (component B), optionally at least a sulfonate group-containing compound (component A3) and optionally at least one trifunctional crosslinking agent as component C1 and / or at least one difunctional chain extender as component C2, wherein component A1 contains 2-methylsuccinic acid or an ester-forming derivative thereof, a process for the preparation of the inventive Polyester, mixtures containing the polyester of the invention; the use of the polyesters or of the mixtures according to the invention for the production of moldings, films, adhesives, foams or fibers and moldings, films, adhesives, foams or fibers containing at least one polyester according to the invention or at least one mixture according to the invention.
  • Biodegradable all aliphatic polyesters based on 2-methyl succinic acid as a comonomer are known in the art.
  • CN 1861660 discloses biodegradable aliphatic copolyesters based on succinic acid and butanediol.
  • succinic acid the copolyesters are based on another aliphatic dicarboxylic acid, adipic acid, methylsuccinic acid, benzylsuccinic acid and 2,2-dimethylsuccinic acid being mentioned.
  • ethylene glycol, propylene glycol or hexanediol can be used as the diols.
  • PBSM a copolyester composed of succinic acid, butanediol and methylsuccinic acid is mentioned
  • Chae et al., Journal of Polymer Science Part B: Polymer Physics, Vol. 9, 1759-1766, 2004 relates to a study of the effect of methyl substitution of the ethylene moiety of poly (butylenesuccinic acid) on the physical properties of the polymers.
  • 2-methylsuccinic acid By adding 2-methylsuccinic acid, the crystallization rate can be slowed down.
  • the addition of 2-methylsuccinic acid in the preparation of an aliphatic copolyester composed of succinic acid and butanediol leads to an improved adjustability of the balance of biodegradability and physical properties.
  • methylsuccinic acid causes deterioration of physical properties and melt processability.
  • EP 0 736 557 A1 relates to aliphatic-aromatic copolyesters which contain repeating units of the following structures,
  • R 11 and R 12 are identical and are selected from the group consisting of C 2 -C 8 alkylene or oxyalkylene, wherein R 11 and R 12 are based on 100% of the diol component;
  • R 13 is selected from one or more members of the group consisting of C 0 -C 8 alkylene or C 2 -C 4 oxyalkylene, wherein R 13 is based on 35 to 95 mole% dicarboxylic acid components; and R 14 is selected from the group consisting of C 6 -C 0 -aryl, where 5 to 65 mole% of R 14 are based on the dicarboxylic acid component.
  • copolyesters there are mentioned the following copolyesters: (1) glutaric acid (30 to 35%), diglycolic acid (0 to 10 mol%), terephthalic acid 25 to 60%), 1,4-butanediol (100 mol%); (2) succinic acid (30 to 85%), diglycolic acid (0 to 10%); Terephthalic acid (5 to 60%), 1, 4-butanediol (100 mol%); (3) adipic acid (30 to 65%), diglycolic acid (0 to 10%), terephthalic acid (25 to 60%), 1,4-butanediol (100 mol%).
  • WO 2006/097354 A1 discloses biodegradable aliphatic / aromatic copolyesters which are 49 to 66 mol% of an aromatic polyfunctional acid, 51 to 34 mol% of an aliphatic acid, of which at least 70% are sebacic acid; and butanediol, as well as mixtures containing these copolyesters.
  • Biodegradable aliphatic / aromatic copolyesters based on 2-methyl-succinic acid as a comonomer have not been described in the prior art.
  • an essential criterion of the aliphatic / aromatic copolyesters is the stability to hydrolysis in order to ensure the use of the aliphatic / aromatic copolyesters and blends and end products based thereon in the widest possible range of applications.
  • Object of the present application over the prior art is therefore to provide biodegradable aliphatic / aromatic copolyesters, which are characterized by improved hydrolytic stability at the same time high proportion of bio-based monomers.
  • component A1 contains 2-methylsuccinic acid and / or an ester-forming derivative thereof.
  • component A1 contains 2-methylsuccinic acid and / or an ester-forming derivative thereof.
  • succinic acid alone, characterized improved hydrolytic stability.
  • aromatic / aliphatic copolyesters in contrast to the pure aliphatic polyesters known from the literature, crystallize sufficiently rapidly at relatively high levels of 2-methylsuccinic acid. They can thus be used in common processing processes.
  • the aliphatic / aromatic copolyesters according to the invention are biodegradable and can be prepared essentially from known and inexpensive monomer building blocks. Furthermore, it is possible by specific modifications to provide chain extension, incorporation of hydrophilic groups and branching groups, tailor-made products for many different applications.
  • the positive properties of the aliphatic / aromatic copolyester are not achieved at the expense of the mechanical properties, ie, the mechanical properties of the copolyesters according to the invention are not impaired by the replacement of succinic acid by 2-methylsuccinic acid. Compared to aliphatic / aromatic copolyesters with a similar proportion of renewable raw materials, the mechanical properties are even improved.
  • biodegradable for a substance or a substance mixture is fulfilled if this substance or the substance mixture has a percentage degree of biodegradation of at least 90% according to DIN EN 13432.
  • the biodegradability leads to this The degradation may be enzymatically, hydrolytically, oxidatively and / or by the action of electromagnetic radiation, for example UV radiation, and for the most part by the action of microorganisms such as bacteria, Biodegradability can be quantified, for example, by mixing polyesters with compost and storing them for a specific time, for example C0 2 -free air by mature compost according to DIN EN 13432 (referring to ISO 14855) during composting and subjected to a defined temperature program.
  • the 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) for maximum C0 2 release of the sample (calculated from the carbon content of the sample) defined as a percentage of biodegradation.
  • Biodegradable polyesters (mixtures) usually show clear degradation phenomena such as fungal growth, cracking and hole formation after only a few days of composting.
  • Component A1 is a repeating unit based on at least one aliphatic dicarboxylic acid and / or an ester-forming derivative thereof, which component contains Al-2-methylsuccinic acid and / or an ester-forming derivative thereof.
  • an ester-forming derivative of a dicarboxylic acid is to be understood as meaning the corresponding di-C 1 -C 4 -alkyl ester, preferably the corresponding di-C 1 -C 6 -alkyl ester, such as dimethyl, diethyl, di-n-propyl, di- iso-propyl, di-n-butyl, di-iso-butyl, di-tert-butyl, di-n-pentyl, di-iso-pentyl and di-n-hexyl esters.
  • Anhydrides of dicarboxylic acids can also be used.
  • component A1 may comprise 2-methylsuccinic acid and / or an ester-forming derivative thereof alone or a mixture comprising
  • Methyl succinic acid and / or an ester-forming derivative thereof with at least one further aliphatic dicarboxylic acid and / or an ester-forming derivative thereof isobutyl succinic acid and / or an ester-forming derivative thereof.
  • Suitable further aliphatic dicarboxylic acids and / or ester-forming derivatives thereof are preferably C 4 -C 30 aliphatic dicarboxylic acids, such as succinic acid, sebacic acid, azelaic acid, adipic acid and brassylic acid, particularly preferably C 6 -
  • the present invention relates to a polyester according to the invention, wherein component A1 comprises a mixture comprising 2-methylsuccinic acid and / or an ester-forming derivative thereof and at least one further dicarboxylic acid and / or an ester-forming derivative thereof selected from the group consisting of succinic acid , Sebacic acid, azelaic acid, adipic acid and brassylic acid, most preferably component A1 comprises a mixture comprising 2-methylsuccinic acid and / or an ester-forming derivative thereof and sebacic acid and / or an ester-forming derivative thereof.
  • the present invention relates to a polyester according to the invention, wherein the component A1 2-methyl succinic acid and / or an ester-forming derivative thereof alone or a mixture comprising 2-methyl succinic acid and / or an ester-forming derivative with at least one other aliphatic C 8 -Ci 3 -Dicarboxylic acid and / or an ester-forming derivative thereof.
  • aliphatic dicarboxylic acids are in particular selected from the group consisting of sebacic acid, azelaic acid, and brassylic acid or ester-forming derivatives understood thereof.
  • the polyester according to the invention is thus based on repeat units of at least one aliphatic dicarboxylic acid and / or an ester-forming derivative thereof as component A1, wherein component A1 is a mixture comprising 2-methylsuccinic acid and / or an ester-forming derivative thereof and at least one another dicarboxylic acid and / or an ester-forming derivative thereof selected from the group consisting of sebacic acid, azelaic acid, adipic acid, brassylic acid and succinic acid.
  • component A1 comprises a mixture comprising 2-methylsuccinic acid and / or an ester-forming derivative thereof and sebacic acid or azelaic acid and / or an ester-forming derivative thereof.
  • component A1 comprises a mixture comprising 2-methylsuccinic acid and / or an ester-forming derivative thereof with at least one further aliphatic dicarboxylic acid and / or an ester-forming derivative thereof
  • the molar fraction of repeating units based on 2-methylsuccinic acid and or an ester-forming derivative of which generally from 5 to 90 mol%, preferably from 10 to 80 mol%, particularly preferably from 20 to 70 mol%.
  • the molar proportion of the at least one further aliphatic dicarboxylic acid and / or an ester-forming derivative thereof is generally from 5 to 95 mol%, preferably from 20 to 90 mol%, particularly preferably from 30 to 80 mol%, the total sum of 2-methylsuccinic acid and / or an ester-forming derivative thereof and the at least one other aliphatic dicarboxylic acid and / or an ester-forming derivative thereof is 100 mol% of the component A1.
  • component A1 has repeat units based on a mixture comprising 5 to 90 mol%, preferably 10 to 80 mol%, particularly preferably 20 to 70 mol% of repeat units based on 2-methylsuccinic acid and / or an ester-forming derivative thereof with 5 to 95 mol%, preferably 20 to 90 mol%, particularly preferably 30 to 80 mol% , Sebacic acid or azealic acid and / or an ester-forming derivative thereof.
  • Succinic, sebacic, azelaic and brassylic acids are derived from renewable resources, e.g. by fermentation or from vegetable oil, e.g. As castor oil, accessible.
  • Component A2 Repeat units based on at least one aromatic dicarboxylic acid and / or an ester-forming derivative thereof are used as component A2.
  • component A2 may be selected from repeating units based on one or more aromatic dicarboxylic acids and / or ester-forming derivatives thereof selected from the group consisting of terephthalic acid, isophthalic acid, 2,5-furandicarboxylic acid, 2,6-naphthoic acid, 1,5-naphthoic acid and Ester-forming derivatives thereof.
  • aromatic dicarboxylic acids mentioned are commercially available.
  • 2,5-furandicarboxylic acid can be obtained from renewable raw materials.
  • Component A2 preferably contains terephthalic acid and / or an ester-forming derivative thereof.
  • component A2 comprises terephthalic acid and / or an ester-forming derivative thereof alone or a mixture comprising terephthalic acid and / or an ester-forming derivative thereof and 2,5-furandicarboxylic acid and / or an ester-forming derivative thereof.
  • Component B comprises terephthalic acid and / or an ester-forming derivative thereof alone or a mixture comprising terephthalic acid and / or an ester-forming derivative thereof and 2,5-furandicarboxylic acid and / or an ester-forming derivative thereof.
  • the polyester according to the invention further contains repeating units based on at least one diol as component B.
  • the component B at least one diol selected from the group consisting of C 2 -C 8 -alkanediols and C 5 -C 0 -cycloalkanediols on.
  • Component B particularly preferably comprises at least one diol selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclopentanediol , 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol and 1, 4-cyclohexanedimethanol.
  • diol selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclopentanediol , 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol and 1, 4-cyclohex
  • the diols mentioned are commercially available.
  • component B contains 1,4-butanediol, it being possible to use 1,4-butanediol alone or in a mixture with one or more further diols, preferably the abovementioned diols.
  • 1, 4-butanediol is also available from renewable raw materials.
  • WO 09/024294 discloses a biotechnological process for producing 1,4-butanediol from different carbohydrates with microorganisms from the class of Pasteurellaceae.
  • Component A3 discloses a biotechnological process for producing 1,4-butanediol from different carbohydrates with microorganisms from the class of Pasteurellaceae.
  • the polyester according to the invention may optionally contain repeating units which are based on at least one sulfonate-containing compound (component A3).
  • the component A3 comprises at least one alkali metal or alkaline earth metal salt of a sulfonate-containing dicarboxylic acid and / or an ester-forming derivative thereof, with particular preference being given to using at least one alkali metal salt of 5-sulfoisophthalic acid as component A3.
  • the sodium salt of 5-sulfoisophthalic acid is used.
  • the polyester may further contain repeating units which are based on at least one trifunctional crosslinking agent as component C1 and / or optionally at least one difunctional chain extender as component C2.
  • Suitable crosslinking agents C1 contain at least 3, preferably 3 to 10, for crosslinking with the carboxyl groups and / or hydroxyl groups, the components A1, A2, B forming the polyester and, if appropriate, A3, suitable functional groups.
  • Suitable functional groups are preferably selected from the group consisting of isocyanate groups, isocyanurate groups, oxazoline groups, epoxide groups, carboxylic anhydride groups, hydroxyl groups, amino groups and carboxyl groups.
  • the crosslinking agent may have at least three identical or different functional groups.
  • Suitable crosslinking agents C1 having at least three functional groups are, for example: tartaric acid, citric acid, malic acid; Trimethylolpropane, trimethylolethane; pentaerythritol; Polyether triols, glycerol, trimesic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid and pyromellitic anhydride. Preference is given to polyols such as trimethylolpropane, pentaerythritol and glycerol, with glycerol being very particularly preferred.
  • Suitable chain extenders are compounds which have two or more, preferably two, functional groups suitable for coupling to the carboxyl groups and / or hydroxyl groups of the polyester-forming components A1, A2, B and A3.
  • the functional groups are preferably selected from the group consisting of isocyanate groups, isocyanurate groups, oxazoline groups, carboxylic anhydride groups and epoxide groups.
  • the functional groups in the chain extender may be the same or different.
  • Chain extenders with at least three functional groups can also be understood as crosslinkers.
  • Aromatic diisocyanates such as tolylene-2,4-diisocyanate, toluylene-2,6-diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthylene 1, 5-diisocyanate and xylylene diisocyanate, with 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate being particularly preferred.
  • Aromatic diisocyanates such as tolylene-2,4-diisocyanate, toluylene-2,6-diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthylene 1, 5-diisocyanate and x
  • the particularly preferred diisocyanates mentioned above are used in the form of mixtures.
  • the diisocyanates may also contain urethione groups, for example, for capping the isocyanate groups.
  • aliphatic diisocyanates can be used as bifunctional chain extenders. Suitable aliphatic diisocyanates are, for. B. linear or branched alkylene diisocyanates or cycloalkylene diisocyanates having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, for. B.
  • Isophorone diisocyanate and 1, 6-hexamethylene diisocyanate are particularly preferably used as aliphatic diisocyanates, with 1,6-hexamethylene diisocyanate being very particularly preferred.
  • the crosslinking agent C1, or chain extender C2 With the aid of the crosslinking agent C1, or chain extender C2, it is possible to build up biodegradable polyesters having a structural viscosity.
  • the theological behavior of the polyester melts improves; the biodegradable polyesters are easier to process, for. B. better by melt consolidation to remove films.
  • the crosslinking agents C1, or chain extenders C2 lead to an increased pseudoplastic behavior, ie. H. the viscosity decreases more sharply under shear compared to polymers without the components C1 or C2.
  • the acid component of the polyester according to the invention is generally of the following structure: a) from 5 to 90 mol%, preferably from 10 to 80 mol%, particularly preferably from 20 to 70 mol%, based on components A1 and A2, of component A1, and b) from 10 to 95 mol%, preferably from 20 to 90 mol%, particularly preferably from 30 to 80 mol%, based on components A1 and A2, of component A2.
  • the polyester according to the invention may contain from 0 to 10 mol% , preferably 0 to 5 mol%, particularly preferably 0 to 3 mol%, based on the sum of components A1 and A2, of at least one sulfonate-containing compound as component A3.
  • the molar amount of component A1 and / or A2 decreases correspondingly in the presence of component A3 so that the total amount of components A1, A2 and A3 gives 100 mol%.
  • the molar amount of the recovery units based on at least one diol as component B corresponds within narrow limits to the sum of the molar amounts of the acid component, ie 98 to 102 mol%.
  • the polyester according to the invention may contain repeating units based on the total amount of components A1, based on 0 to 3 wt.%, Preferably 0.05 to 2 wt.%, Particularly preferably 0.1 to 1.5 wt. A2, B and optionally A3, at least one crosslinking agent as component C1 and / or at least one chain extender as component C2.
  • the present invention relates to a polyester containing repeating units based on:
  • an acid component A comprising: a) from 10 to 90 mol%, preferably from 10 to 80 mol%, particularly preferably from 20 to 70 mol% of component A1, preferably 2- methylsuccinic acid and / or an ester-forming derivative as component A1 thereof alone or a mixture comprising 2-methylsuccinic acid and / or an ester-forming derivative thereof and at least one further dicarboxylic acid and / or an ester-forming derivative thereof selected from the group consisting of sebacic acid, azelaic acid, adipic acid and brassylic acid, preferably sebacic acid ; b) 10 to 90 mol%, preferably 20 to 80 mol%, particularly preferably 30 to 80 mol% of component A2, wherein as component A2 preferably terephthalic acid and / or an ester-forming derivative thereof is used, c) 0 to 10 mol%, preferably 0 to 5 mol%, particularly preferably 0 to 3 mol% of the component A3, where as component A3
  • Sulfoisophthalic acid is used, d) 98 to 102 mol%, based on the acid component A of component B, wherein as component B preferably 1, 4-butanediol is used, and e) 0 to 3 wt .-%, preferably 0.05 to 2 wt .-%, particularly preferably 0, 1 to 1, 5 wt .-% of the component C1 and / or C2, being particularly preferably used as component C1 glycerol.
  • the polyesters according to the invention generally have a number average molecular weight M n of 5,000 to 100,000 g / mol, preferably 10,000 to 60,000 g / mol, particularly preferably 20,000 to 40,000 g / mol, determined by GPC on PMMA standard in hexafluoroisopropanol.
  • the weight-average molecular weight M w is generally 30,000 to 300,000 g / mol, preferably 60,000 to 200,000 g / mol, particularly preferably 80,000 to 150,000 g / mol.
  • the polydispersity index M w / M n is generally 1 to 6, preferably 2 to 4.
  • the aliphatic-aromatic polyesters according to the invention are generally random copolyesters, ie the incorporation of the aromatic and aliphatic diacid units is purely random.
  • the distribution and length of the individual blocks can be calculated according to B. Vollmert, ground plan of macromolecular chemistry. As described by Wtt et al. in J. Environ. Pole. Degradation, Vol. 4, No. 1 (1996), p. 9, degradation in compost of n> 3 aromatic model oligomers is normally very slow. In aliphatic-aromatic polyesters, however, block structures are degraded rapidly.
  • the polyesters of the invention generally have an acid number measured according to DIN EN 12634 of ⁇ 1, 0 mg KOH / g.
  • the polyesters of the invention have a melt volume rate (MVR) according to ISO 1133 is generally from 0.5 to 30 cm 3/10 min. (190 ° C, 2, 16 kg weight).
  • the viscosity number of the polyesters according to the invention according to DIN 53728 is generally at least 80 cm 3 / g, preferably 160 to 250 cm 3 / g, particularly preferably 170 to 220 cm 3 / g.
  • the polyesters according to the invention are generally prepared by reacting the components A1, A2 and B and, if appropriate, the components A3 and, if appropriate, C1 or C2, with one another.
  • polyesters according to the invention are preferably prepared in a two-stage reaction cascade (as described, for example, in WO 2009/127555 and WO 2009/127556).
  • the dicarboxylic acids or ester-forming derivatives of dicarboxylic acids (components A1 and A2 together with the reacted at least one diol (component B) in the presence of a transesterification catalyst to a prepolyester.
  • Zinc, aluminum or titanium catalysts are generally used as transesterification catalysts, with titanium catalysts being preferred.
  • Suitable titanium catalysts are, for. Tetra (isopropyl) orthotitanate and tetrabutyl orthotitanate (TBOT).
  • the titanium catalysts have the advantage over the tin, antimony, cobalt and lead catalysts frequently used in the prior art that residual amounts of the catalyst or secondary products of the catalyst remaining in the product are less toxic. This fact is important in the case of the biodegradable polyesters according to the invention, since they are released directly into the environment, for example as composting bags or mulch films.
  • dicarboxylic acids and / or ester-forming derivatives thereof are initially condensed in the presence of at least one diol (component B) and optionally in the presence of the crosslinker C1, generally in the presence of the transesterification catalyst.
  • a molar excess of diol is used in relation to the dicarboxylic acids (sum of components A1 and A2).
  • a melt of the resulting prepolyester is generally condensed at an internal temperature of 200 to 250 ° C within usually 3 to 6 hours while distilling off the liberated diol. This is generally done at a pressure below normal pressure.
  • polyesters can then optionally be chain-extended and / or crosslinked according to methods known to those skilled in the art with the addition of component C2. Suitable methods are described in WO 96/15173 and EP-A 0 488 617.
  • the chain extension is generally carried out at reaction temperatures of 220 to 270 ° C, preferably 230 to 250 ° C, usually at atmospheric pressure or overpressure.
  • the residence times in the continuous process are generally 2 to 30 minutes.
  • a suitable continuous process for the preparation of the polyesters according to the invention is, for. As described in WO 2009/127556.
  • the polyesters according to the invention can also be prepared in a batch process.
  • the components A1, A2, B, optionally A3 and optionally C1 mixed in any Dosier Horn tile and condensed to form a prepolyester.
  • From the Prepolyester is - optionally with the aid of at least one chain extender C2 - produced a polyester having the desired viscosity.
  • polyesters according to the invention can be processed excellently. They are characterized in particular by an excellent hydrolytic stability.
  • the biodegradable polyesters according to the invention, or the polyester mixtures mentioned below may contain further ingredients. Suitable ingredients are known in the art.
  • the biodegradable polyesters according to the invention, or the polyester mixtures mentioned below can be used in additives customary in plastics technology, such as stabilizers; nucleating agents; Neutralizing agents; Lubricants and release agents such as stearates (especially calcium stearate); 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 agents; UV absorbers; UV stabilizers; Antifog agents and / or dyes.
  • the additives can generally be used in amounts of from 0 to 5% by weight, preferably from 0.1 to 2% by weight, based on the total amount of the polyester according to the invention.
  • Plasticizers may be present in the polyesters according to the invention or the polyester mixtures specified below in from 0.1 to 10% by weight, based on the amount of the polyester according to the invention.
  • biodegradable polyesters according to the invention are suitable for the preparation of, preferably biodegradable, polymer blends.
  • Suitable polymer blends of biodegradable polyesters are generally known to the person skilled in the art.
  • polyester mixtures comprising i) at least one polyester according to the invention
  • polyester mixtures wherein in the polyester mixtures at least one of the components mentioned under ii) or iii) is present.
  • the present invention relates to biodegradable polyester mixtures comprising i) from 5 to 95% by weight, preferably from 20 to 80% by weight, based on the components i and ii, of at least one inventive polyester;
  • iii 0 to 90 wt .-%, preferably 1 to 80 wt .-%, and particularly preferably 2 to 50 wt .-%, based on the components i and ii, of at least one organic and / or inorganic filler and / or nanoparticulate filler; and iv) 0 to 2 wt .-%, preferably 0.05 to 1, 5 wt .-%, based on the components i and ii, of at least one compatibilizer.
  • polylactic acid is preferably suitable.
  • Polylactic acid having the following property profile is particularly preferably used:
  • a melt volume rate (MVR at 190 ° C. and 2.16 kg according to ISO 1133 of 0.5 to 30, preferably 2 to 18 ml / 10 minutes)
  • Preferred polylactic acids are, for example, NatureWorks ® 2003, 3001, 3051, 3251, 4020, 4032 or 4043D (polylactic acid from NatureWorks ® or NL-Naarden and USA Blair / Kansas).
  • a suitable polycaprolactone is z.
  • Suitable polyhydroxyalkanoates are, for. As poly-4-hydroxybutyrate and poly-3-hydroxybutyrate. Furthermore, the copolyesters of the abovementioned hydroxybutyrates are suitable with 3-hydroxyvalerates or 3-hydroxyhexanoates.
  • Poly-3-hydroxy-butyrate-co-4-hydroxybutyrate is z.
  • Poly-3-hydroxybutyrate-co-3-hydroxyhexanoate is z. B. from P & G or Kaneka known.
  • Poly-3-hydroxybutyrate is z. B. PH B Industrial under the brand name Biocycle ® and Tianan sold under the name Inmat ®.
  • Suitable polyhydroxyalkanoates generally have a molecular weight M w of from 100,000 to 1,000,000 g / mol, preferably from 300,000 to 600,000 g / mol.
  • Suitable polyalkylene are z. For example, polyethylene carbonate and polypropylene carbonate.
  • polyesters based on aliphatic diols and aliphatic and / or aromatic dicarboxylic acids are in the context of the present application also polyester derivatives such as polyether esters, polyester amides or polyetheresteramides.
  • polyester derivatives such as polyether esters, polyester amides or polyetheresteramides.
  • suitable polyesters based on aliphatic diols and aliphatic and / or aliphatic / aromatic dicarboxylic acids are, for. B. linear, non-chain extended polyesters, as described in WO 92/09654.
  • polyesters of butanediol, terephthalic acid and aliphatic C 6 -C 8 -dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid and brassylic acid.
  • Such polyesters are for.
  • WO 2006/097353, WO 2006/097354, WO 2006/097355 and WO 2006/097356 Preferred are chain-extended and / or branched polyesters based on aliphatic diols and aliphatic and / or aliphatic / aromatic dicarboxylic acids. These are z.
  • polyesters based on aliphatic diols and aliphatic or aliphatic / aromatic dicarboxylic acids are Ecoflex ® (BASF SE), Eastar Bio ® and origo-Bi ® (Novamont).
  • Suitable organic fillers are preferably selected from the group consisting of native or plasticized starch, native or plasticized amylose, natural fibers, wood flour, crushed cork, ground bark, nutshells, ground press cake (vegetable oil refinery), dried production residues from the fermentation or distillation of beverages , like beer, brewed sodas (eg Bionade), wine or sake.
  • Suitable inorganic fillers are, for. B.
  • Suitable nanoparticulate fillers are e.g. selected from the group of phyllosilicates (montmorillonites) or silicas having a mean particle diameter of ⁇ 500 nm.
  • Starch and amylose can be natively, i. H. non-thermoplasticized, or be thermoplasticized with plasticizers such as glycerol or sorbitol (see EP-A 0 539 541, EP-A 0 575 349, EP-A 0 652 910).
  • modified starches e.g., cationically and / or anionically modified or carboxymethyl starches
  • plasticizers such as glycerine or sorbitol.
  • Natural fibers are generally understood as meaning cellulose fibers, hemp fibers, sisal, kenaf, jute, flax, abaca, coconut fibers or regenerated cellulose fibers (rayon) such as cordenka fibers.
  • 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 ⁇ , more preferably 8 to 15 ⁇ on.
  • the fiber length in the polymer mixtures is generally 20 ⁇ m to 1000 ⁇ m, preferably 180 to 500 ⁇ m and particularly preferably 200 to 400 ⁇ m.
  • the fibrous fillers can be better compatibility with the polyester of the invention z. B. be pretreated surface with a silane compound.
  • Suitable compatibilizers which are used in particular for compatibility mediation between the polyester of the invention and the polymers mentioned under ii) are z.
  • carboxylic anhydrides such as maleic anhydride, epoxy group-containing copolymers based on styrene, acrylic esters and / or methacrylic esters or peroxides.
  • the epoxy group-bearing units are preferably glycidyl (meth) acrylate.
  • the epoxy-containing copolymers of the above type are sold for example by BASF Resins BV under the trademark Joncryl ® ABR. Peroxides those marketed by the company Akzo Nobel under the name "Trigonox”.
  • a particularly suitable compatibilizer is such. As “Joncryl ADR4368 ®” or "Trigonox 301".
  • polyesters according to the invention or the polyester mixtures according to the invention can be used for the production of moldings, coating compositions, fibers, films, foams, adhesives. Furthermore, the polyester or polyester mixtures according to the invention for use as mulch films, as a packaging material for seeds and nutrients, as a substrate in adhesive films, baby pants, bags, sheets, bottles, boxes, dust bags, labels, pillowcases, protective clothing, toiletries, handkerchiefs and Toy suitable.
  • a particularly preferred field of application relates to the use of the polyester and polyester mixtures according to the invention for the production of films and film tapes for nets and fabrics, tubular films, chill-roll films with and without orientation in a further process step, with and without metallization or SiO x coating.
  • the polyester and polyester mixtures according to the invention can be further processed into tubular films, shrink films and stretch films.
  • Possible applications are bottomed folding bags, side seam bags, carry bags with handle holes, shrink labels or shirt carrier bags, inliners, heavy bags, freezer bags, compost bags, agricultural films (mulch films), film bags for food packaging, peelable sealing films - transparent or opaque - weldable closure films - transparent or opaque - , Sausage casings, salad foil, cling film (stretch film), eg for fruits, vegetables, meat and fish, stretch wrap for wrapping of pallets, films for nets, packaging films, e.g. for snacks, chocolate and cereal bars, peelable lidding films, e.g. for dairy packaging (yoghurt, cream, etc.), fruits and vegetables, semi-rigid packaging, e.g. for smoked sausage and cheese.
  • the polyester and polyester blends of the invention are particularly suitable for packaging meat, poultry, meat products, processed meats, sausages, smoked sausages, seafood, fish, crabmeat, cheese, cheese products , Desserts, pies, z.
  • meat-fish-poultry-tomato filling, 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 food; Jams and jellies; Spreads, chocolate cream; and ready meals. Further information for suitable applications are z. B. in "Food Processing Handbook", James G. Brennan, Wley-VCH, 2005.
  • the polymer blends according to the invention have after extrusion to single or multi-layered tube, blown or press films excellent tensile strength (according to ENISO 6383
  • the tear propagation resistance is a very important product property, above all in the area of thin (hose) films for, for example, bio-waste bags or thin-walled carrier bags (eg shirt pockets, fruit bags) Importance of mulch films in the agricultural sector.
  • biodegradable polyester and polyester mixtures according to the invention also have very good adhesive properties. This makes them ideal for coating paper, eg. B. for paper cups and paper plates. For their production, both the extrusion coating and lamination process is suitable. A combination of these methods or a coating by spraying, knife coating or dipping is conceivable.
  • the amounts of dimethyl terephthalate (DMT), 1, 4-butanediol (1, 4-BDO), tetrabutyl orthotitanate (TBOT) and glycerol given in Tables 1 and 2 are initially charged in a glass flask with stirrer and distillation bridge. While stirring, the mixture is heated and distilled off the liberated methanol at temperatures up to about 180 ° C. After completion of the distillation, the amounts indicated in Table 1 or 2 of the respective aliphatic dicarboxylic acids (2-methylsuccinic acid (2-MeBS), succinic acid, adipic acid, sebacic acid) are added, the internal temperature is slowly increased to 220 ° C and distilling off the liberated water.
  • DMT dimethyl terephthalate
  • 1, 4-butanediol 1, 4-butanediol
  • TBOT tetrabutyl orthotitanate
  • glycerol glycerol
  • the molecular weights Mn and Mw of the aliphatic / aromatic polyesters are determined according to DIN 55672-1. Eluent: hexafluoroisopropanol (HFIP) + 0.05 wt% trifluoroacetic acid K salt; the calibration is done with narrow polymethyl methacrylate standards.
  • HFIP hexafluoroisopropanol
  • the determination of the viscosity numbers is carried out according to DIN 53728 Part 3, January 3, 1985, Kapillarviskosimetrie.
  • a micro-Ubbelohde viscometer, type M-II, is used.
  • the solvent used is the mixture: phenol / o-dichlorobenzene in a weight ratio of 50/50.
  • melt volume index (MVR) [cm 3 / 10min] is measured according to DIN 53735 or ISO 1 133 at the specified temperature and load.
  • DSC measurements are carried out on a DSCT apparatus from Mettler-Toledo (type DSC 30). Approximately 15 mg of the sample are weighed and measured with the following temperature profile:
  • T k crystallization temperature, defined as the maximum of the crystallization peak of the first cooling curve.
  • T kk cold crystallization temperature, defined as the maximum of the crystallization peak in the approximate temperature range of 25-35 ° C during the second heating curve.
  • T g glass transition temperature, determined from the second heating curve
  • Tsmp.max Melting temperature, defined as the maximum of the melting peak during the second heating curve in the temperature range of approx. 100-150 ° C.
  • Table 3 Analysis of Examples 1 to 10 (according to the invention)
  • Examples 5 to 10 according to the invention show a significantly increased rate of crystallization compared with Examples 1 to 4 according to the invention.
  • An increased crystallization rate is eg when processed to z. As blown films, extrusion foils with optionally subsequently deep-drawn moldings, injection-molded articles, paper coatings desirable.
  • hydrolysis stability of some selected examples and comparative examples is determined by storage of press films produced at 70 ° C. in dist. Water checked. The decrease in the chain length of the polyesters is monitored by the decrease in the viscosity number over 20 days. From Table 5 it can be seen that Examples 4, 6 and 8 according to the invention have a significantly lower decrease in the viscosity number and thus a significantly higher hydrolysis resistance than Comparative Examples 1 and 8.
  • the 100-micron-thick film is tested qualitatively according to EN 13432 for its disintegration in the compost and meets the requirements of EN 13432 after the end of the test. Further film pieces of 30 microns thick film at 58 ° C for 6 months in humidified compost (Fwitzkompst Kompostierwerk Frankenthal) buried. After 180 days, no traces of the pieces of film can be found, which proves the biodegradability of the polyester 11.

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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 un polyester contenant des motifs répétitifs à base d'au moins un acide dicarboxylique aliphatique ou d'un dérivé de celui-ci formant un ester (composant A1), au moins un acide dicarboxylique aromatique ou d'un dérivé de celui-ci formant un ester (composant A2), au moins un diol (composant B), facultativement au moins un composé contenant des groupes sulfonate (composant A3) ainsi que facultativement au moins un agent de réticulation trifonctionnel en tant que composant C1 et/ou au moins un agent d'allongement de chaîne difonctionnel en tant que composant C2, le composant A1 contenant de l'acide 2-méthylsuccinique ou un dérivé de celui-ci formant un ester. L'invention concerne également un procédé de production du polyester de l'invention ; des mélanges contenant le polyester de l'invention ; l'utilisation du polyester de l'invention ou des mélanges de l'invention pour produire des pièces moulées, des films, des adhésifs, des mousses ou des fibres ; ainsi que des pièces moulées, des films, des adhésifs, des mousses ou des fibres contenant au moins un polyester selon l'invention ou au moins un mélange selon l'invention.
EP12710701.9A 2011-03-23 2012-03-21 Polyester à base d'acide 2-méthylsuccinique Withdrawn EP2688956A1 (fr)

Priority Applications (1)

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EP12710701.9A EP2688956A1 (fr) 2011-03-23 2012-03-21 Polyester à base d'acide 2-méthylsuccinique

Applications Claiming Priority (3)

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EP11159338 2011-03-23
PCT/EP2012/054935 WO2012126921A1 (fr) 2011-03-23 2012-03-21 Polyester à base d'acide 2-méthylsuccinique
EP12710701.9A EP2688956A1 (fr) 2011-03-23 2012-03-21 Polyester à base d'acide 2-méthylsuccinique

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CN112979899A (zh) * 2019-12-16 2021-06-18 高鼎精密材料股份有限公司 高反拨弹性生质水性pu树脂与配方开发技术
EP3885390A1 (fr) 2020-03-25 2021-09-29 Covestro Deutschland AG Procédé de fabrication d'un étherestérol

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