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WO2009019118A1 - Procédé de fabrication d'un copolymère multiséquencé - Google Patents

Procédé de fabrication d'un copolymère multiséquencé Download PDF

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Publication number
WO2009019118A1
WO2009019118A1 PCT/EP2008/059394 EP2008059394W WO2009019118A1 WO 2009019118 A1 WO2009019118 A1 WO 2009019118A1 EP 2008059394 W EP2008059394 W EP 2008059394W WO 2009019118 A1 WO2009019118 A1 WO 2009019118A1
Authority
WO
WIPO (PCT)
Prior art keywords
solvent
poly
multiblock copolymer
reaction
macromonomers
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.)
Ceased
Application number
PCT/EP2008/059394
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German (de)
English (en)
Inventor
Jens Boden
Monique Hannemann
Michael Zierke
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.)
GKSS Forshungszentrum Geesthacht GmbH
Original Assignee
GKSS Forshungszentrum Geesthacht GmbH
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 GKSS Forshungszentrum Geesthacht GmbH filed Critical GKSS Forshungszentrum Geesthacht GmbH
Publication of WO2009019118A1 publication Critical patent/WO2009019118A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/14—Powdering or granulating by precipitation from solutions
    • 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
    • C08G2280/00—Compositions for creating shape memory
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the invention relates to a process for preparing a multiblock copolymer which is composed of at least two different oligoester, oligoether and / or oligoether ester blocks.
  • the multiblock copolymer preferably has shape memory properties, that is, it is capable of storing and restoring at least one temporary shape in the "shape memory" after a corresponding programming of a permanent shape.
  • shape memory polymers SMPs (shape memory polymers) which, when induced by a suitable stimulus, show a shape transition from a temporary shape to a permanent shape according to a prior programming. Most often, this shape memory effect is thermally stimulated, that is, when heated, the polymer material on the defined switching temperature takes place driven by Entropieelastiztician provision.
  • Shape memory polymers are often multiblock copolymers, which are mostly composed of two thermodynamically incompatible segments (macromonomers A and B).
  • the blocks A and B must each have a minimum molecular weight and a minimum proportion, so that a phase separation of the blocks in the polymer is ensured.
  • Multiblock copolymers form physical crosslinks.
  • the responsible for it Phase is called hard segment and has the highest thermal transition temperature in the system.
  • the next lower thermal transition temperature phase is the phase defining the switching segment and is responsible for switching the thermally induced shape memory effect to the switching temperature, which substantially corresponds to its transition temperature.
  • the chemical structure of multiblock copolymers is generally characterized by a statistical sequence of the macromonomers A and B.
  • Multiblock copolymers are prepared by polyaddition or polycondensation of the macromonomers A and B.
  • Teng et al. discloses a multiblock copolymer composed of poly ( ⁇ -caprolactone) and poly (L-lactide) blocks.
  • the polymer is prepared from the PCL diisocyanate ( ⁇ , ⁇ -macrodiisocyanate) and the PLLA diol ( ⁇ , ⁇ -macrodiol).
  • the coupling reaction of the end group-functionalized macromonomers takes place from the melt.
  • multiblock copolymers which are composed of PPDO or PCL as soft segment and poly ( ⁇ -caprolactone-glycolide) (CG) or poly (alkyleneadipinate) (AD) as a hard segment.
  • the multiblock copolymers are prepared from the corresponding macrodiols with TMDI as the linking unit in dichloroethane.
  • the known preparation processes for AB multiblock copolymers are generally achieved by coupling the ⁇ , ⁇ -macrodiols having number-average molecular weights below 10,000 g / mol with the isomer mixture 2,2 (4), 4- Trimethylhexane-1, 6-diisocyanate (TMDI) in 1, 2-dichloroethane takes place.
  • TMDI Trimethylhexane-1, 6-diisocyanate
  • the syntheses so far only take place on a laboratory scale with product quantities of a few 100 g.
  • the known methods are subject to various problems and not suitable to be readily transferred to a larger production scale, such as the Kleintechnikumoncestab.
  • the working-up method of precipitation from the highly diluted polymer solution used in the prior art requires the use of very large amounts of the precipitant and also of large vessels, which likewise precludes scale-up.
  • the quantities of precipitant required for a product quantity of 1 kg of polymer solids are in the cubic meter range and require 2-3 t mixers as a container.
  • the method should in particular also allow a scale-up in the Kleintechnikumoncestab.
  • the process according to the invention for preparing a hydrolytically degradable multiblock copolymer composed of at least two different oligoester, oligoether and / or ON-goether ester blocks comprises the steps: a) providing at least two different, ⁇ , ⁇ -functionalized macromonomers of the group of oligoesters, oligoethers and / or oligoether esters, in particular ⁇ , ⁇ -macrodiols, b) coupling the ⁇ , ⁇ -functionalized macromonomers by reaction with an aliphatic diisocyanate as Coupling reagent in a high-boiling, halogen-free solvent or solvent mixture and c) workup of the multiblock from the reaction mixture, wherein in a first step, the precipitation of the multiblock copolymer is carried out by lowering the temperature and in a second step, the solvent or solvent mixture is withdrawn.
  • halogen-free high-boiling solvents for carrying out the coupling of the two macromonomers, it is initially achieved that the hazardous potentials of the chlorinated solvents used in the prior art are largely eliminated.
  • halogen-free solvents have a much lower corrosion potential, so that plants can be used, which are common in the laboratory and Kleintechnikumaddstab.
  • the solvents chosen must have good solubility for the macromonomers used as well as the product polymer. Solvents such as 1, 3-dioxolane, 1, 4-dioxane, toluene, dimethyl carbonate (dimethyl carbonate), diethyl carbonate (diethyl carbonate) or mixtures of these have proven to be suitable, for example.
  • high-boiling solvents or solvent mixtures are understood to have a boiling point of at least 90 ° C. This allows the implementation of the coupling reaction at temperatures above 80 0 C, in particular at 85 0 C, whereby a corresponding acceleration of the reaction can be achieved. Preference is given to using solvents or mixtures thereof which have a boiling point of at least 100 ° C. It has also been found, surprisingly, that halogen-free solvents lead to halogenated solvents, such as 1, 2-dichloroethane, to accelerate the reaction. As a result, undesirable side reactions can be avoided and low polydispersities can be achieved.
  • a cleavage of chorus or phosgene is excluded, which also lead to undesirable side reactions, for example as a result of peroxide formation.
  • diisocyanates are used as coupling reagent, which have a high reactivity.
  • an aliphatic diisocyanate is used which is selected from the group comprising 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI), 2,2,4-trimethylhexane-1,6-diisocyanate, 2,4,4-trimethylhexane-1, 6-diisocyanate or a mixture of these.
  • HDI 1,6-hexanediisocyanate
  • reaction time of the coupling step can thus be reduced to a few days.
  • the preparation of the product polymer from the reaction mixture by a combined precipitation freeze-drying process wherein in a first step, the precipitation of the multiblock copolymer is carried out by lowering the temperature and in a second step, the solvent or solvent mixture is withdrawn.
  • the (still hot) reaction solution is introduced into a template at very low temperatures, in particular in a template of inexpensive liquid nitrogen, which leads to a sudden precipitation and freezing of the product polymer, which is obtained in particular as fine granules.
  • an intensive stirring is preferably carried out in the nitrogen template, whereby a particularly fine granulation of the multiblock copolymer is achieved.
  • the frozen granules are lat / solvent mixture exposed to a vacuum, so that the solvent is removed.
  • this step is carried out at such low temperatures that the solvent sublimates, that is, passes directly from the solid (frozen) state of matter into the gaseous state.
  • suitable solvents non-solvent
  • the required amounts of solvent are significantly reduced in the process according to the invention.
  • the workup is preferably carried out even without the addition of a precipitant.
  • the precipitation of the multiblock copolymer is carried out by adding a solvent or solvent mixture "in excess" to the initially hot reaction solution, in which the polymer is largely insoluble, but the amount used is significantly below that in the prior art usual quantities. Due to the elevated temperature, however, complete precipitation of the polymer does not yet occur, but as a rule only slight clouding of the reaction solution, that is to say the formation of a suspension. Suitable precipitants (non-solvents) have proven to be n-butyl acetate, tert-butyl acetate, dibutyl ether or methanol, for example. Subsequently, as described above, the actual precipitation is carried out by lowering the temperature.
  • a further advantage of the method according to the invention is the fact that due to the shorter reaction time and the associated reduction of undesirable side reactions, in principle multiblock copolymers with higher molecular weights than the prior art can be represented.
  • preference is given to producing polymers having number average molecular weights M n of at least 30,000 g / mol, preferably of at least 35,000 g / mol.
  • macromonomers come used, which have a number average molecular weight M n of at most 10,000 g / mol.
  • Preferred macromonomers are selected from the group comprising poly (p-dioxanone) (PPDO), poly (pentadecalactone) (PPDL), poly ( ⁇ -caprolactone) (PCL), poly (D, L-lactide), poly (L-) Lactide, poly (glycolic acid) and poly (ethylene glycol).
  • Example 1 Preparation of an HDI-Coupled PPDO / PCL Multiblock Copolymer
  • the reactor was equipped with a spiral stirrer (1/2 beba manual mixer type B050 made of stainless steel), a stirring motor (Heidolph), a circulating cooler (15 0 C, Julabo), a circulating thermostat (85 0 C, Julabo MW, MC 4 or MC 6 ), an intensive cooler made of glass (SCHOTT), and a mechanical seal (HWS) with Doppelkardanwelle.
  • a spiral stirrer 1/2 beba manual mixer type B050 made of stainless steel
  • a stirring motor Heidolph
  • a circulating cooler (15 0 C, Julabo)
  • a circulating thermostat 85 0 C, Julabo MW, MC 4 or MC 6
  • an intensive cooler made of glass SCHOTT
  • HWS mechanical seal
  • the reaction was terminated when at least one of the abovementioned molecular weight limit values (here after exactly 3 days), by adding the reaction solution with about 0.5 g of 1, 8-octanediol and 1, 5 I n-butyl acetate at 85 0 C bath temperature and was mixed well for about 2 h at 85 0 C, wherein a milky turbidity of the hot reaction solution occurred, that is, the precipitation of the polymer product began.
  • the 1, 8-octanediol served the Abretician of possibly unreacted isocyanate groups.
  • the suspension was also pumped at 85 0 C via a (valveless) wobble piston metering pump from the reaction vessel in a filled with liquid nitrogen 5-liter plastic cup made of PP.
  • the polymer solution should have a consistency which allows the solution to drop into the precipitant at the selected metering rate (0.2-0.5 l / min).
  • the quantitative precipitation of the polymer then took place, which was immediately obtained as frozen granules and additionally comminuted by intensive stirring with a paint disperser (IKA).
  • IKA paint disperser
  • the resulting granules were separated from the liquid nitrogen by Abdekanntieren and Drain on a filter bag made of PP fleece.
  • the frozen granules were dried in PP photo cups in a freeze-drying process to constant weight.
  • a PPDO / PCL multiblock copolymer was prepared according to the reaction procedure described in Example 1, except that the coupling reagent used was TMDI instead of HDI with otherwise identical molecular parameters.
  • the reaction time was about 8 weeks until the above-mentioned molecular weight criteria were satisfied and the coupling reaction was stopped.
  • a PPDL / PCL multiblock copolymer was prepared according to the reaction procedure described in Example 1 using HDI as a coupling reagent. The reaction time was 3 days until the above-mentioned molecular weight criteria were satisfied and the coupling reaction was stopped.
  • a PPDL / PCL multiblock copolymer was prepared according to Example 3, except that TMDI instead of HDI was used as the coupling reagent under otherwise identical molecular parameters as a coupling reagent.
  • the reaction time was about 8 weeks until the above-mentioned molecular weight criteria were satisfied and the coupling reaction was stopped.
  • the following tables list molecular, thermal and mechanical properties of the PPDO / PCL multiblock copolymers which are prepared according to Examples 1 and 2 by coupling with 1,6-hexanediisocyanate (hexamethylene diisocyanate, HDI) (Table 1) or with 2,2 ( 4), 4-trimethylhexane-1,6-diisocyanate (TMDI) (Table 2), and the PPDL / PCL multiblock copolymers prepared according to Examples 3 and 4 prepared by coupling with HDI and TMDI, respectively (Table 3) were produced.
  • the molecular, thermal and mechanical properties of the polymers fulfill the requirements for functionalization of the multiblock copolymers as shape memory materials. In particular, it was shown that very high molecular weights were achieved with relatively low polydispersities PD.

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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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un copolymère multiséquencé, qui est composé d'au moins deux séquences oligoester, oligoéther et/ou oligoétherester différentes, ledit procédé comprenant les étapes consistant à : (a) préparer au moins deux macromonomères a,?-fonctionnalisés différents du groupe des oligoesters, oligoéthers et/ou oligoétheresters, (b) coupler les macromonomères a,?-fonctionnalisés par réaction avec un diisocyanate aliphatique en tant que réactif de couplage, de préférence avec HDI, dans un solvant ou un mélange de solvants sans halogène de point d'ébullition élevé et (c) récupérer le copolymère multiséquencé à partir du mélange réactionnel, notamment par un procédé combiné de précipitation-lyophilisation, selon lequel dans une première étape la précipitation du copolymère multiséquencé est réalisée par diminution de la température et dans une seconde étape le solvant ou le mélange de solvant est éliminé.
PCT/EP2008/059394 2007-08-03 2008-07-17 Procédé de fabrication d'un copolymère multiséquencé Ceased WO2009019118A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007037063.8 2007-08-03
DE200710037063 DE102007037063B4 (de) 2007-08-03 2007-08-03 Verfahren zur Herstellung eines Multiblockcopolymers

Publications (1)

Publication Number Publication Date
WO2009019118A1 true WO2009019118A1 (fr) 2009-02-12

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PCT/EP2008/059394 Ceased WO2009019118A1 (fr) 2007-08-03 2008-07-17 Procédé de fabrication d'un copolymère multiséquencé

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WO (1) WO2009019118A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE102010028192A1 (de) 2010-04-26 2011-10-27 Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH Verfahren zur Rückstellung eines, ein Formgedächtnis-Kompositmaterial aufweisenden Artikels

Citations (1)

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Publication number Priority date Publication date Assignee Title
WO1999042528A2 (fr) * 1998-02-23 1999-08-26 Mnemoscience Gmbh Polymeres a memoire de forme

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GB2155264A (en) 1984-03-02 1985-09-18 Standard Telephones Cables Ltd Amplifier circuits for radio receivers
WO1999042147A1 (fr) 1998-02-23 1999-08-26 Massachusetts Institute Of Technology Polymeres biodegradables a memoire de forme
AU768478B2 (en) * 1999-04-16 2003-12-11 Rutgers, The State University Porous polymer scaffolds for tissue engineering
WO2003088818A2 (fr) 2002-04-18 2003-10-30 Mnemoscience Gmbh Sutures polymeres a memoire de forme biodegradables
DE10217350C1 (de) 2002-04-18 2003-12-18 Mnemoscience Gmbh Polyesterurethane
CN1166715C (zh) * 2002-08-23 2004-09-15 清华大学 一种可生物降解聚氨酯弹性体的合成
DE10316573A1 (de) 2003-04-10 2004-11-04 Mnemoscience Gmbh Blends mit Form-Gedächtnis-Eigenschaften
TWI248947B (en) * 2003-07-21 2006-02-11 Ind Tech Res Inst Biodegradable copolymer, and polymeric micelle composition containing the copolymer

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Publication number Priority date Publication date Assignee Title
WO1999042528A2 (fr) * 1998-02-23 1999-08-26 Mnemoscience Gmbh Polymeres a memoire de forme

Non-Patent Citations (2)

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Title
MIN C ET AL: "BIODEGRADABLE SHAPE-MEMORY POLYMER-POLYLACTIDE-CO-POLY(GLYCOLIDE-CO-C APROLACTONE) MULTIBLOCK COPOLYMER", 1 August 2005, POLYMERS FOR ADVANCED TECHNOLOGIES, WILEY & SONS, BOGNOR REGIS, GB, PAGE(S) 608 - 615, ISSN: 1042-7147, XP001239616 *
TENG C ET AL: "Synthesis and characterization of poly(L-lactic acid)-poly( epsilon caprolactone) multiblock copolymers by melt polycondensation", 1 January 2004, JOURNAL OF POLYMER SCIENCE - PART A - POLYMER CHEMISTRY, WILEY & SONS, HOBOKEN, NJ, US, PAGE(S) 5045 - 5053, ISSN: 0887-624X, XP002458623 *

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DE102007037063B4 (de) 2012-12-06

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