EP1495063A1 - Procede de production d'homopolyesters ou de copolyesters d'esters et/ou de diesters cycliques - Google Patents

Procede de production d'homopolyesters ou de copolyesters d'esters et/ou de diesters cycliques

Info

Publication number
EP1495063A1
EP1495063A1 EP03722283A EP03722283A EP1495063A1 EP 1495063 A1 EP1495063 A1 EP 1495063A1 EP 03722283 A EP03722283 A EP 03722283A EP 03722283 A EP03722283 A EP 03722283A EP 1495063 A1 EP1495063 A1 EP 1495063A1
Authority
EP
European Patent Office
Prior art keywords
formula
polymerization
initiator
radicals
aryl
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Withdrawn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
EP03722283A
Other languages
German (de)
English (en)
Inventor
Gerald Rafler
Inna Bechthold
Horst Rieckert
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.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Schill and Seilacher AG
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Schill and Seilacher AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV, Schill and Seilacher AG filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP1495063A1 publication Critical patent/EP1495063A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • the invention relates to a process for the preparation of melt-stable homo- and copolyesters by ring opening polymerization of the corresponding cyclic monomers, e.g. the cyclic diester of lactic acid, in the presence of an initiator / stabilizer system.
  • Homo- and copolyesters of L- and D, L-lactic acid are biodegradable polymer materials with thermoplastic processing and
  • Application properties can be used in a variety of ways as packaging plastic, in hygiene products, for disposable articles, but also as a surgical implant material or galenic auxiliary for parenteral drug delivery systems.
  • An indispensable prerequisite for the use of these homo- or copolyesters in all the fields of application mentioned are constant product properties at the molecular level, such as molar mass and molar mass distribution for the homo- and copolyesters, maintenance of chirality in the case of poly-L-lactic acid or comonomer ratio and comonomer distribution in the Trap the copolyester. Under technical conditions, this constancy of product properties can only be achieved with synthesis processes that can be safely controlled or with efficient additives.
  • L, L- or D, L-dilactide Organometallic compounds of tin are preferably used to initiate or catalyze this polymerization reaction (see, for example, J. Dahlmann, G. Rafler: Acta Polymerica 44 (1993) 103 and cited therein).
  • initiator in the ring opening polymerization is also largely determined by the substrate to be polymerized.
  • Cyclic monoesters such as caprolactone, or cyclic carbonates, such as 1,3-dioxan-2-one (trimethylene carbonate)
  • 1,3-dioxan-2-one trimethylene carbonate
  • 1,4-dioxane-2,5-dione diglycolide
  • Rafler Acta Polymerica 44 (1993) 168
  • they can therefore be used without problems in the presence of the initiators mentioned in US Pat. No. 5,484,881 or elsewhere can be polymerized (cf.
  • tin-containing initiators preferably the tin-ll-octonoate most commonly used in accordance with the prior art, cause a reaction profile which is difficult to master from a technical point of view, with an extremely steep increase at the start of the reaction, an undefined molecular weight maximum and a pronounced degradation of the polymer Running through the maximum (cf. E. Dahlmann, G. Rafler: Acta Polymerica 44 (1993) 107).
  • This profile of the temporal development of the molar mass which is unsuitable for an industrial process, is highly concentration-dependent, whereby in contrast to ionically and radically initiated polymerization processes of olefins, at least for the majority of the tin-initiated polymerizations, turnover and molar mass in the ring-opening polymerization are synchronous, i.e. H. high polymerization rate and high conversion also lead to high molecular weights. Ring-chain equilibrium and heterochain character of the polymers formed determine their molecular and thus also their deformation and application properties. Especially the
  • the equilibrium character of this special polymerization and the associated tendency to regress of the cyclic monomer by depolymerization is also initiated or activated by the initiator.
  • This behavior of the initiators not only complicates the manageability of the synthesis process, but also leads to considerably disruptive depolymerizations with a corresponding reduction in the molar mass during the thermoplastic processing of the polymers.
  • the monomer formed in the back reaction also leads to a considerably faster and uncontrollable hydrolysis of the polymer in Presence of moisture and thus an undesirable impairment of the possible uses of the polymers.
  • Nonspecific thermooxidative and hydrolytic degradation reactions are inhibited by water-binding additives (hydrolysis), such as carbodiimides, activated acid derivatives or isocyanates (cf., for example, US Pat. No. 6,005,068).
  • water-binding additives such as carbodiimides, activated acid derivatives or isocyanates (cf., for example, US Pat. No. 6,005,068).
  • the long-known phosphites eg Ultranox RTM 626) or sterically hindered phenols are also used as antioxidants in US Pat. No. 6,005,068, preference being given to commercially available IRGANOX types.
  • the ring opening polymerization should proceed faster in the presence of these antioxidants, and significantly higher molar masses should be achieved, as will be shown with the aid of Example 13.
  • the polymer should be able to be stabilized against degradation reactions during extraction of monomer in vacuo, as in Example 11 shown.
  • monomer regression cannot be achieved in this way when the polymer is processed:
  • radical scavengers such as Irganox or Ultranox when remelting already polymerized samples from which the monomer had been extracted causes a new formation of monomer (see Table 13 in comparison to Table 12 of US Pat. No. 6,005,068).
  • Initiator combinations based on organotin and organotitanium compounds which intervene differently in ring opening polymerization and cyclizing depolymerization, act in a very different reaction mechanistic manner, but with a very good effect.
  • the depolymerization can be suppressed under bulk polymerization conditions, the extreme character of the polymerization profiles largely overcome and the process can thus be made more reliable (see DE 101 13 302.2).
  • melt-stable homo- and copolyesters which are based on cyclic esters of L. - and allow D, L-lactic acid and other cyclic monomers, in particular further cyclic esters, to be polymerized, to be produced discontinuously or continuously in differently designed plant equipment and to be processed without monomer regression.
  • Molecularly particularly uniform products should preferably result, regardless of the polymerization conditions.
  • the ring opening polymerization is carried out in the presence of known organotin initiators, if appropriate in the presence of further initiators and / or stabilizers based on metals of subgroup IV, in particular based on titanium or zirconium.
  • organotin initiators if appropriate in the presence of further initiators and / or stabilizers based on metals of subgroup IV, in particular based on titanium or zirconium.
  • reducing agents may be added during production, preferably when or shortly before the desired degree of polymerization is reached, but above all during subsequent thermoplastic deformation, which largely or completely suppress the reversibility of the reaction.
  • R 1 and R 2 are each independently hydrogen, alkyl, aryl or heteroaryl and X is -OR 3 or -NR1R 2 , where R 3 is hydrogen, alkyl, aryl, M 1 or AM 11 with M 1 is alkali metal ion and M 11 is alkaline earth metal ion and the radicals Ri and R 2 have the meaning given above.
  • radicals R 2 and R 3 or radicals R 1 and R 2 together with the phosphorus and optionally with the nitrogen or oxygen atom can also form a saturated or unsaturated heterocycle, for example
  • Ri H, alkyl, aryl, heteroaryl or
  • cyclic starting compounds which can be polymerized to polyesters under the influence of tin-containing polymerization catalysts or initiators are suitable for the polymerization and stabilization process according to the invention.
  • These can be, for example, cyclic esters, in particular mono- or diesters, such as dilactide or caprolactone.
  • cyclic esters in particular mono- or diesters, such as dilactide or caprolactone.
  • dilactide or caprolactone With regard to their chemical structure, their number and their quantitative proportions, these can be used in any way and may contain further components.
  • the procedure according to the invention not only allows the ring opening polymerization to be reliably controlled by the adjustability of a stable molar mass level (cf.example 3 and FIG.
  • the stabilization of the molecular weight according to the invention by organophosphorus additives based on phosphinates can be carried out both in batch production, e.g. in stirred reactors or kneaders, as well as in continuous processes in vertical or horizontal reactors.
  • Reactive extrusion processes in co-rotating twin-screw extruders are particularly efficient, in which the dosing of the melt stabilizer is particularly simple and the homogeneous distribution of the additive in the highly viscous polyester melt poses no difficulties.
  • the additive is preferably incorporated at a point in time at which the reaction has reached the desired degree of conversion.
  • the additive is preferably metered in at a location where the polymer is short of leaving the reactor, e.g. shortly before the discharge zone of a (screw) extruder.
  • the additives according to the invention can be metered in either directly as a pure substance, in solution or in the form of a masterbatch with the polymer or else with the monomer.
  • the initiator / stabilizer system is also used for the synthesis of statistical and non-statistical binary or ternary copolymers by ring-opening polymerization.
  • the statistical copolyesters are produced by simultaneous addition (discontinuous) or metering (continuous) of the monomeric esters or diesters.
  • Non-statistical copolyesters are obtained with the gradual addition of comonomer or preferably by reactive compounding of the homopolyesters in reactors of high mixing intensity, such as kneaders or twin-screw extruders.
  • tin compounds for the initiator / stabilizer system are, for example, tin ll carboxylates, tin IV alkoxides, dialkoxy tin oxides, trialkoxy tin hydroxides and tin IV aryls.
  • Initiator combinations of tin with organo-soluble titanium or zirconium compounds can also be used. Suitable for this combination are, for example Alkoxides of titanium and zirconium, such as titanium IV acetylacetonate, zirconium octonoate or zirconium acetylacetonate.
  • the concentration of the initiator / stabilizer system according to the invention can be freely selected within wide limits, but the stabilizer must be used at least equimolar to the initiator. Otherwise, the concentration of initiator and stabilizer depends primarily on the technological requirements of the system and the application-specific material requirements, preferably material and deformation properties, which are largely determined by the molar mass and its distribution. The preferred concentration range for the
  • Polymerization initiator is 10 "5 - 10 " 3 mol / mol monomer unit; the stabilizer is used in the stabilizer / initiator ratio of 2: 1 to 10: 1, preferably in concentrations of 0.01-0.1 mass%.
  • the polymerization temperature can also be varied within a relatively wide range. Temperatures of 180 ° C-225 ° C can be selected for the polymerization of the L, L-dilactide without disruptive degradation reactions. Due to the lower softening temperature, lower polymerization temperatures, starting at 125 ° C., can also be used for the polymerization of the D, L-dilactide.
  • reaction temperatures above the polymer melting temperature can be freely selected in a wide range in the presence of the initiator / stabilizer system according to the invention.
  • the model studies on the degradation behavior of the polylactides were carried out in the aqueous phase.
  • pressed test specimens measuring 10 * 10 * 1 mm were stored in phosphate-buffered solution and the mass was determined gravimetrically after drying and the molar mass was determined by gel chromatography after different times.
  • the monomer content was determined for the poly-D, L-lactides by falling over from dimethylformamide / methanol and for the poly-L-lactides by extraction with methanol. 1 shows the in vitro degradation of poly-D, L-lactide as a function of the monomer content at 37 ° C.
  • the rate of hydrolytic degradation of amorphous poly-L-lactide obtained by melt quenching corresponds to that of racemate (Table 1).
  • the extraction is carried out with methanol in a Soxhiet apparatus; for reprecipitation, the sample is dissolved in dimethylformamide and the polymer precipitated in methanol.
  • Turnover gravimetric
  • molar mass gel chromatography
  • L, L-dilactide is polymerized in the presence of 5 * 10 "5 mol / mol Sn (oct) 2 at 195 ° C and with 0.01% by mass 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide The course with a reduced initiator concentration is shown in Fig. 4.
  • Stabilized poly-L-lactide has a high molecular uniformity, as shown in Table 2.
  • the mixed monomer melt becomes the initiator Sn (oct) 2 (5 * 10 "5 mol / mol in the form of a 0.1% solution in toluene) and after a further 7.5 min 0.36 g of the melt stabilizer 9,10-dihydro-9-oxa-10-phosphaphen-anthrene-10-oxide (UKANOL DOP) are added and the melt is thoroughly mixed in the kneader in a closed system at 195 ° C. for 25 minutes the polymer melt is discharged via the screw, cooled on a conveyor belt by blowing with cold air and granulated by means of a strand pelletizer. The polymer pellet is extracted with methanol and then dried in vacuo.
  • Sn (oct) 2 5 * 10 "5 mol / mol in the form of a 0.1% solution in toluene
  • UOP melt stabilizer 9,10-dihydro-9-oxa-10-phosphaphen-anthrene-10-oxide
  • the melt stabilizer 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (UKANOL DOP) is continuously the polymer melt before the discharge zone of the extruder fed.
  • the average residence time of the polymerizing lactide melt in the extruder is approx. 10
  • the polymer melt is cooled on a conveyor belt by blowing with cold air and granulated by means of a strand granulator.
  • the polymer granulate is extracted with methanol and then dried in vacuo.
  • the poly (L-lactide (75) -co-caprolactone (25)) is demonomerized by falling over from dimethylformamide / water. After drying at 80 ° C. in vacuo, 3700 g of copolymer with an average molecular weight of 112,000 g / mol are obtained.
  • Example 3-9 Melt-stabilized polylactide produced in accordance with Example 3-9 is extracted exhaustively with methanol and, after drying to constant weight (residual moisture ⁇ 0.02%), processed into test bars (shoulder bar, isostab) in an injection molding machine (type ARBURG Allrounder 270 M). The recovered monomer is determined gravimetrically from the test bars by extraction with methanol (Table 3).

Landscapes

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

Abstract

L'invention concerne un procédé de production d'homopolyesters et de copolyesters d'acide lactique stables en fusion et de monomères comparables, par polymérisation par ouverture de cycle d'esters ou de diesters cycliques, en présence d'un système d'initiateurs/de stabilisants. Les initiateurs ou catalyseurs organo-étains habituels sont utilisés pour la polymérisation par ouverture de cycle. La stabilisation en fusion est obtenue au moyen d'additifs organophosphoriques spécifiques avec des degrés d'oxydation faibles du phosphore. Les additifs organophosphoriques peuvent être utilisés directement lors de la production de ces polyesters ou être ajoutés aux polymères lors d'un processus de compoundage ultérieur.
EP03722283A 2002-04-16 2003-04-11 Procede de production d'homopolyesters ou de copolyesters d'esters et/ou de diesters cycliques Withdrawn EP1495063A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10216834 2002-04-16
DE10216834A DE10216834A1 (de) 2002-04-16 2002-04-16 Verfahren zum Herstellen schmelzestabiler Homo- und Copolyester cyclischer Ester und/oder Diester
PCT/DE2003/001241 WO2003087191A1 (fr) 2002-04-16 2003-04-11 Procede de production d'homopolyesters ou de copolyesters d'esters et/ou de diesters cycliques

Publications (1)

Publication Number Publication Date
EP1495063A1 true EP1495063A1 (fr) 2005-01-12

Family

ID=29224499

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03722283A Withdrawn EP1495063A1 (fr) 2002-04-16 2003-04-11 Procede de production d'homopolyesters ou de copolyesters d'esters et/ou de diesters cycliques

Country Status (4)

Country Link
US (1) US20050165206A1 (fr)
EP (1) EP1495063A1 (fr)
DE (1) DE10216834A1 (fr)
WO (1) WO2003087191A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101306539B1 (ko) * 2005-10-05 2013-09-09 데이진 가부시키가이샤 폴리락트산 조성물
JP2007099939A (ja) * 2005-10-05 2007-04-19 Teijin Ltd ポリ乳酸を含有する組成物
EP3009477B1 (fr) 2006-07-20 2024-01-24 Orbusneich Medical Pte. Ltd Composition polymère bioabsorbable pour un dispositif médical
US7959942B2 (en) 2006-10-20 2011-06-14 Orbusneich Medical, Inc. Bioabsorbable medical device with coating
CN101631513B (zh) 2006-10-20 2013-06-05 奥巴斯尼茨医学公司 可生物吸收的聚合物组合物和医疗设备
AT506040B1 (de) * 2007-11-14 2012-03-15 Jungbunzlauer Austria Ag Partikuläre katalysator- und katalysator/stabilisator-systeme zur herstellung hochmolekularer homo- und copolyester von l-, d- oder d,l-milchsäure
AT506038B1 (de) * 2007-11-14 2015-02-15 Jungbunzlauer Austria Ag Verfahren zur herstellung zyklischer diester von l-, d- und d,l-milchsäure
EP2832762A1 (fr) * 2013-07-30 2015-02-04 Sulzer Chemtech AG Procédé de fabrication de poly (acide 2-hydroxyalcanoïque) et poly (acide 2-hydroxyalcanoïque)) pouvant être obtenu par ce procédé
CN110194833B (zh) * 2018-02-26 2020-10-27 中国科学技术大学 用于引发丙交酯开环聚合的催化剂体系与聚乳酸的制备方法

Family Cites Families (8)

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US6005068A (en) * 1992-10-02 1999-12-21 Cargill Incorporated Melt-stable amorphous lactide polymer film and process for manufacture thereof
US5338822A (en) * 1992-10-02 1994-08-16 Cargill, Incorporated Melt-stable lactide polymer composition and process for manufacture thereof
US5770682A (en) * 1995-07-25 1998-06-23 Shimadzu Corporation Method for producing polylactic acid
DE19537365C1 (de) * 1995-10-06 1996-12-19 Fraunhofer Ges Forschung Verfahren zur Stabilisierung der Schmelzeviskosität von Zinn-, Titan- und/oder Zirkoniumverbindungen als Katalysator und/oder Initiator enthaltender aliphatischer oder aromatisch-aliphatischer Homo- oder Copolyester und Verwendung einer Verbindung, die mindestens einen Tropolonring aufweist als Maskierungsmittel in Polyesterschmelzen
DE19847137A1 (de) * 1998-10-13 2000-04-20 Schill & Seilacher Verwendung von DOP als Antioxidations-, Alterungsschutz- und Arzneimittel
US6245880B1 (en) * 1999-10-08 2001-06-12 Toyo Boseki Kabushiki Kaisha Organophosphorous composition, method of producing organophosphorous compound, polyester composition and method of producing the same
GB2369824B (en) * 2000-09-11 2004-08-04 Nat Inst Of Advanced Ind Scien Method of producing aliphatic polyester and product obtained thereby
DE10113302B4 (de) * 2001-03-19 2009-09-24 Fraunhofer-Gesellschaft für die angewandte Forschung e.V. Verfahren zur Herstellung von Homo- und Copolyestern der Milchsäure

Non-Patent Citations (2)

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See also references of WO03087191A1 *

Also Published As

Publication number Publication date
DE10216834A1 (de) 2003-11-13
WO2003087191A1 (fr) 2003-10-23
US20050165206A1 (en) 2005-07-28

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