WO2008068072A1 - Procédé de production d'un copolymère à blocs multiples alternés à mémoire de forme - Google Patents

Procédé de production d'un copolymère à blocs multiples alternés à mémoire de forme Download PDF

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WO2008068072A1
WO2008068072A1 PCT/EP2007/059583 EP2007059583W WO2008068072A1 WO 2008068072 A1 WO2008068072 A1 WO 2008068072A1 EP 2007059583 W EP2007059583 W EP 2007059583W WO 2008068072 A1 WO2008068072 A1 WO 2008068072A1
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macromonomer
pcl
mol
end group
alternating
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PCT/EP2007/059583
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German (de)
English (en)
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Andreas Lendlein
Günter Malsch
Hans-Jürgen KOSMELLA
Helmut Kamusewitz
Steffen Kelch
Nico Scharnagl
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Gkss-Forschungszentrum Geesthacht Gmbh
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Publication of WO2008068072A1 publication Critical patent/WO2008068072A1/fr

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66Polyesters containing oxygen in the form of ether groups
    • C08G63/664Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08Lactones or lactides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10Definition of the polymer structure
    • C08G2261/12Copolymers
    • C08G2261/126Copolymers block
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2280/00Compositions for creating shape memory
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78Preparation processes
    • C08G63/81Preparation processes using solvents

Definitions

  • the invention relates to a method for producing a shape memory polymer, which - in addition to a permanent mold - can store at least one temporary shape.
  • the polymer is an alternating multiblock copolymer having a structure consisting of the alternating successive macromonomers A and B.
  • 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 the programmed polymer material is heated above the defined transition temperature, the return driven by entropy elasticity takes place.
  • Shape memory polymers are typically polymer networks in which chemical (covalent) or physical (noncovalent) crosslinks determine the permanent shape.
  • the programming is carried out by deforming the polymer material above the transition temperature of a switching segment and then cooling it down while maintaining the deformation forces under this temperature in order to fix the temporary shape. Reheating above the transition temperature results in a phase transition of the switching segment defining phase and restoration of the original permanent shape.
  • Shape memory polymers are usually random 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.
  • Statistical multiblock copolymers form physical crosslinks.
  • the responsible phase is called hard segment and has the highest thermal transition temperature T tran s A in the system.
  • the phase with the next lower thermal transition temperature T tra ns B is that which determines the switching segment. de phase and is for switching the thermally induced shape memory effect with the switching temperature T SC hait B) responsible.
  • Statistical multiblock copolymers are prepared by polyaddition or polycondensation of the macromonomers A and B.
  • the chemical structure of these multiblock copolymers is generally characterized by a statistical sequence of the macromonomers A and B. This results in a different number of repeat units A and B within the multiblocks and thus a heterogeneous distribution of each coupled blocks of the same type (-AA- or -BB-) or other type (-AB-) (eg AABABBBAB).
  • a distinction is made between (strictly) alternating multiblock copolymers, which are characterized by an alternating sequence of blocks A and B and accordingly have the structure - (AB) n -. Alternating multiblock copolymers with shape memory have not been realized so far.
  • 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 at variable mass ratios of the segments, so that statistical multiblock copolymers are to be expected. It will be the influence of Composition and molecular weight on the thermal behavior and the crystalline properties studied, while the mechanical properties and shape memory behavior is not reported.
  • the dipole component with increased solubility and reactivity, in particular at low conversions, is intensified incorporated the multiblock copolymer.
  • the resulting non-uniformity of the chemical composition contributes to irregularities of the microstructure.
  • no homogeneous mixing of the two macromonomers A and B can be ensured, so that there are different concentration ratios of the components in the different partial volumes of the melt.
  • the invention is therefore based on the object to provide a method for producing a multi-block copolymer with shape memory, which leads with high reliability to an alternating sequence of blocks A and B or to a homogeneous distribution of sequence / nit narrow length distribution and thus produces polymer products which have an improved performance profile in terms of SM effect and mechanical properties.
  • This object is achieved by a process for producing an alternating multiblock copolymer with shape memory properties which has a structure consisting of the alternately successive macromonomers A and B, with the following steps:
  • end functionalization creates electrophilic and nucleophilic reaction centers so that an alternating "crossover coupling" is achieved by their reaction in the second process stage.
  • Targeted selection of the two end groups and the preparation of the correspondingly functionalized macromonomers A and B in step (a) can minimize reactivity differences of the macromonomers and preclude interfering influences on the homogeneity of the coupling steps in step (b).
  • the multiblock copolymer resulting from the process has a largely regular AB block structure in which the macromonomers A and B follow one another alternately according to the structure (AB) n . To achieve this, on the one hand, it has proved essential to have the strictest possible stoichiometry
  • step (b) to maintain the nucleophilic end group of the macromonomer A and the electrophilic end group of the macromonomer B in step (b), that is to set a molar ratio of the nucleophilic end group to the electrophilic end group of 1, with a maximum molar deviation of ⁇ 8 mol% still tolerable has been found.
  • the reliability of the process can be further increased if the molar deviation from the stoichiometric ratio is at most ⁇ 5 mol%, in particular at most ⁇ 3 mol%.
  • this measure ensures - unlike the implementation in melt - a homogeneous mixing of the reactants, so that ideally in each subvolume of the reaction mixture corresponding concentrations of the macromonomers A and B are present.
  • the number-average molecular weights M n of the end group-functionalized macromonomers A and B are matched as far as possible for their reaction in step (b).
  • a difference between the degrees of polymerization of the macromonomers A and B is set, which is at most 15%, in particular at most 10%, preferably at most 5%, based on the number-average degree of polymerization P n of the heavier macromonomer.
  • the resulting multiblock copolymer has thermally inducible shape memory properties, that is, it is capable of assuming at least a temporary shape as well as a permanent form depending on the temperature.
  • one of the blocks A or B of the switching segment determining block with defined thermal transition temperature and the other block of the hard segment determining block can store a shape in the "shape memory".
  • both blocks A and B can contribute to the construction of switching segment-forming phases that form mutually different transition temperatures, so that two temporary shapes are programmable in addition to the permanent shape.
  • switching segment is understood to mean a phase in the solid polymer whose structure is defined by the macromonomers A and B used in the synthesis.
  • the formation of a separate phase by phase separation in the solid is thus the basis for the formation of the typical material properties of the corresponding compound.
  • the polymer system as a whole has material properties that can be assigned to the respective blocks.
  • the switching temperatures for the thermally induced effect may in particular be glass transition or melting temperatures.
  • an advantageous embodiment of the invention provides that the number average molecular weight M n of the alternating multiblock copolymer in the range of 10,000 to 50,000 g / mol, in particular in the range of 20,000 to 40,000 g / mol, while the preferred weight average molecular weight M w of the alternating Multiblockcopolymers in the range of 40,000 to 80,000 g / mol, in particular in the range of 50,000 to 70,000 g / mol.
  • M n of the alternating multiblock copolymer in the range of 10,000 to 50,000 g / mol, in particular in the range of 20,000 to 40,000 g / mol
  • M w of the alternating Multiblockcopolymers in the range of 40,000 to 80,000 g / mol, in particular in the range of 50,000 to 70,000 g / mol.
  • higher molecular weights are necessary for achieving good mechanical properties and a highly reproducible SM effect.
  • the number average molecular weight M n is defined by Equation 1 and the weight average molecular weight M w by Equation 2, where M, the molecular weight of the polymer type i means n, the number of all produced polymers with the molecular weight M, and n the total number of polymers.
  • the switching temperatures of the alternating multiblock copolymers lie in a narrower temperature range than the statistical counterparts. This means a sharper and well-defined transition.
  • the polymers of the invention have an increased modulus of elasticity (modulus of elasticity) over the random polymers. In particular, on average, an E-modulus is achieved which is larger by one order of magnitude than in the case of the corresponding random multiblock copolymers at comparable elongation at break ( ⁇ max ⁇ 1000%).
  • a hydroxyl group is used in step 1 of the method as the nucleophilic end group, that is, the nucleophile end phenomenonfunktionalinstrumente macromonomer A is an ⁇ , ⁇ -diol.
  • the electrophilic end group can advantageously be used isocyanate group.
  • the electrophilic end group-functionalized macromonomer B is an ⁇ , ⁇ -diisocyanate.
  • isocyanates readily react with hydroxyl groups and on the other hand can be prepared in good yield from the commercially available .alpha.,. Omega.-diols.
  • isocyanates have comparable reactivities to hydroxyl groups, which, as already explained above, favors the construction of an alternating and homogeneous product structure.
  • the ⁇ , ⁇ -diisocyanate of the macromonomer B is particularly preferably provided in step 1 by reacting the corresponding ⁇ , ⁇ -diol of the macromonomer B with an isocyanate alkane.
  • the reaction can be carried out with a Diisocyanatalkan, for example, with 1, 6-diisocyanato-2,2,4-trimethylhexane or 1,6-diisocyanato-2,4,4-trimethylhexane (TMDI), a mixture of isomers of these or 1,6 - Diisocyanatohexane (HDI).
  • a molar ratio of isocyanate groups to hydroxyl groups of at least 20: 1, preferably at least 50: 1 is set.
  • one of the macromers A or B is a polyether of the formula II (poly (p-dioxanone), PPDO), the formula III (poly (ethylene oxide), PEO), the formula III (poly (tetrahydrofuran), PTHF), the formula V (poly (propylene oxide))) or a derivative of these, in which one or more of the hydrogen radicals of the methylene units (-CH 2 -) are replaced by unbranched or branched, saturated or unsaturated C 1 to C 6 radicals ,
  • the abovementioned macromers according to the formulas II to V generally function as switching segments ("soft segments") in the corresponding multiblock copolymers.
  • a polyester of the formula I, in particular PCL is used as a first macromonomer, and a polyether of the formula II, in particular PPDO, as a second macromonomer.
  • the PCL with the electrophilic end group can be functionalized on both sides, in particular with isocyanate groups ( ⁇ , ⁇ -PCL diisocyanate), and the PPDO with the nucleophilic end group, in particular with hydroxyl groups ( ⁇ , ⁇ -PPDO-diol).
  • ⁇ -PPD0 diisocyanate can be reacted with ⁇ , ⁇ -PCL diol.
  • a macromonomer of the formula I with n ⁇ 5 and a macromonomer of the formula I with n> 10 are converted to an alternating multiblock copolymer after the functionalization has taken place.
  • the macromonomer of the formula I with n ⁇ 5 is preferably provided with an electrophilic end group (in particular diisocyanate) and macromonomer of the formula I where n> 10, preferably with a nucleophilic end group (in particular diol).
  • a further aspect of the present invention relates to a multiblock copolymer which can be prepared by the process according to the invention and which has the described advantageous material properties.
  • FIG. 1 shows the chemical process steps for producing an alternating multiblock copolymer according to a first embodiment of the invention, in which the ⁇ , ⁇ -macrodiisocyanate of PCL is reacted with the ⁇ , ⁇ -macrodiol of PPDO;
  • Figure 2 shows the chemical process steps for producing an alternating multiblock copolymer according to a first embodiment of the invention, in which the ⁇ , ⁇ -macrodiisocyanate of PCL is reacted with the ⁇ , ⁇ -macrodiol of PPDO;
  • Figure 2 shows the chemical process steps for producing an alternating
  • a multiblock copolymer according to a second aspect of the invention wherein the ⁇ , ⁇ -macrodiisocyanate of PPDO is reacted with the ⁇ , ⁇ -macrodiol of PCL;
  • FIG. 3 shows FTIR spectra of PCL after different reaction times of the diisocyanation
  • FIG. 6 1 H-NMR spectrum of the alternating multiblock copolymer PCL-10K-bl
  • FIG. 7 1 H-NMR spectrum of the alternating multiblock copolymer PCL-2K-bl
  • FIG. 8 shows a stress-strain diagram of an alternating poly- (PCL-old)
  • Figure 9 shows time courses of the temperature and the elongation of an alternating
  • PCL poly ( ⁇ -caprolactone)
  • PPDO poly (p-dioxanone)
  • the synthesis takes place in two steps, the diisocyanation of one of the two macromonomer diols taking place in the first step, and the reaction of the ⁇ , ⁇ macrodiisocyanate thus produced with the ⁇ , ⁇ macrodiol of the other macromonomer by crossover Clutch.
  • the ⁇ , ⁇ -macrodiisocyanate of PCL can be reacted with the ⁇ , ⁇ -macrodiol of PPDO (Example 1) or the ⁇ , ⁇ -macro-diisocyanate of PPDO with the ⁇ , ⁇ -macrodiol of PCL (Example 2).
  • an ⁇ , ⁇ -diisocyanate alkane preferably 1,6-diisocyanato-2,4,4-trimethylhexane (TMDI)
  • TMDI 1,6-diisocyanato-2,4,4-trimethylhexane
  • the reaction can advantageously be supported catalytically by a suitable catalyst.
  • the diisocyanatizations of the .alpha.,. Omega.-macrodiols of PCL and PPDO necessitate an adaptation of the reaction instructions in order to obtain the desired reaction products because of the distinctly different solubility.
  • the crossover coupling in the second process stage of ⁇ , ⁇ -PCL diisocyanate and ⁇ , ⁇ -PPDO-diol (Example 1) or ⁇ , ⁇ -PPDO diisocyanate and ⁇ , ⁇ -PCL diol (Example 2) is under a stoichiometric (molar) ratio of the NCO and OH groups of the macromonomers used.
  • concentrations of the end groups are calculated assuming the fullest possible ⁇ , ⁇ -end functionalization of the macro-diisocyanates to be coupled from the number average molecular weight M n . Thereafter, an equimolar incorporation rate of the macromonomers is given in the multiblock copolymer.
  • Example 1 Preparation of a PCL-PPDO multiblock copolymer from the ⁇ , ⁇ -macro-diisocyanate of PCL and the ⁇ , ⁇ -macrodiol of PPDO
  • PCL-macrodiol with isocyanate end groups is carried out according to the reaction shown in Figure 1 (1st step).
  • TMDI 1, 6-diisocyanato-2,4,4-trimethylhexane
  • THF tetrahydrofuran
  • PCL macrodiol PCL 3.3 K: prepared from ⁇ -caprolactone from Sigma Aldrich, PCL 2K and PCL 1 OK from Sigma Aldrich
  • the concentration of TMDI in the template is adjusted so that there is a 50-fold molar excess of TMDI with respect to the PCL macrodiol with respect to the completed reaction mixture.
  • the reaction mixture is heated to about 60 0 C and stirred under argon atmosphere at this temperature over a period of 24-72 h. This is facilitated by the good solution behavior of PCL in THF - a temperature control, under which during the addition at low temperature, the reaction is suppressed and after increasing the temperature, a uniform reaction start. Subsequently, the PCL diisocyanate is precipitated from the solution, washed extensively, dried under vacuum to constant weight and stored cooled.
  • PCL macrodiols with molecular weights of 2,000 g / mol (PCL 2K), 3,300 g / mol (PCL 3.3K) and 10,000 g / mol (PCL 10K).
  • PCL 2K 1,3 g / mol
  • PCL 3.3K 3,300 g / mol
  • PCL 10K 10,000 g / mol
  • the products were subjected to comprehensive analysis of FTIR spectroscopy, 1 H NMR spectroscopy, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC).
  • FIG. 3 The FTIR spectra recorded as a function of the reaction time are shown in FIG. 3, while FIG. 4 shows as reference the FTIR spectra of PCL macrodiol (PCL 1 R), and PCL macro diisocyanate (PCL 1 R-NCO) and TMDI.
  • PCL 1 R PCL macrodiol
  • PCL 1 R-NCO PCL macro diisocyanate
  • TMDI TMDI
  • the reaction mixture and the polymer solution is maintained at about 70 0 C to keep the PPDO-diol in solution.
  • concentration of TMDI in the template is adjusted so that there is a 50-fold molar excess of TMDI over the PPDO macrodiol with respect to the completed reaction mixture.
  • the reaction mixture is stirred at about 70 0 C under an argon atmosphere over a period of 48 h.
  • the self-adjusting turbidity of the solution persists throughout the reaction time.
  • the PPDO diisocyanate is precipitated from the solution, washed extensively, dried under vacuum to constant weight and stored refrigerated.
  • the products were subjected to comprehensive analysis of FTIR spectroscopy, 1 H NMR spectroscopy, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC).
  • the "crossover coupling" of the two macromers is carried out under strict equimolarity of the end group concentration of the two reactants and the molecular weights M n of the PCL macrodiisocyanates used are adjusted.
  • the second reaction step of the crossover coupling of the ⁇ , ⁇ -PPDO diisocyanate with the ⁇ , ⁇ -PCL diol shown in FIG. 2 (2nd step) is catalyzed with a suitable catalyst.
  • a suitable catalyst for this purpose, the dissolved in DCE ⁇ , ⁇ -PPDO diisocyanate is heated to 70 ° C under argon atmosphere and stirring. This is followed by the dropwise addition of dissolved in DCE ⁇ , ⁇ -PCL diol.
  • 20% by weight PCL and 10% by weight PPDO solutions are used for this reaction.
  • the reaction takes place at 70 0 C over a period of from 24 h.
  • the product with anhydrous and cooled to -30 0 C di- ethyl ether is precipitated and dried to constant weight.
  • reaction products were characterized chemically by means of 1 H-NMR spectroscopic analysis (FIGS. 6 and 7), thermally by means of DSC (Table 2), mechanically by means of tensile strain measurements and the shape memory properties by means of cyclic, thermo-mechanical investigations (FIGS. 8 and 9). characterized.
  • PCL (mol%) PCL, dd / (PCL, dd + PPDO, dd).
  • PCL-1 OK-bl-PPDO-1.5K (FIG. 6)
  • a PCL fraction of 84.5 mol% and for PCL-2K-bl-PPDO-1.5K (FIG. 7) of 53.5 mol% % determined.
  • Table 2 shows the enthalpies ⁇ H determined in DSC measurements on selected poly (PCL-old-PPDO) multiblock copolymers according to the present invention of different composition. It can be stated that there is a significant dependence of the enthalpy of fusion on the crystalline parts of the PCL as well as the PPDO block segment. In particular, an approach of the enthalpies of fusion of the PCL segment to the enthalpy of fusion of the pure PCL-10K macrodiol as a reference sample can be observed with increasing PCL content. Analogously, this applies to the enthalpies of fusion of the PPDO-1, 5K segment.
  • the elastically beginning, visco-elastic stretching region A shows a significant increase in stress at low elongation of up to 10%.
  • area B which extends to an elongation of about 200%, occurs purely plastic strain (so-called "necking behavior"), wherein the material "flows" without voltage increase.
  • the subsequent third region C which extends to an elongation of about 1000%, is characterized by the proportionality between stress and strain.
  • the sample annealed at 55 ° C. for 48 h exhibits viscoelastic deformation in the initial range up to about 200% elongation, while in the further course up to 1000% elongation an analogous behavior to that of the untempered sample is observed.
  • the maximum tensile strength ⁇ max , the maximum elongation ⁇ max and the modulus of elasticity decrease with increasing temperature.
  • the comparison of the thermomechanical characteristics of the alternating poly (PCL-old-PPDO) multiblock copolymers prepared according to the invention with the statistical variants of comparable composition also shows that the former have comparable values for ⁇ max and ⁇ max at lower molecular weights.
  • the alternating multiblock copolymers have distinctly higher moduli of elasticity than their statistical reference patterns, which indicates an influence on the materials produced according to the invention by the formation of a molecular superstructure.
  • the quantities for quantifying the SM behavior can be determined.
  • the elongation fixing ratio R f is determined from the ratio of the elongation of the fixed sample and the real maximum elongation ⁇ m applied for fixing.
  • the average of the cycles in Figure 9 is R f (1-3) 96%.
  • the strain recovery ratio R r of the Nth cycle can be calculated from ⁇ m and the strain after recovery in the previous (N-1) th cycle. Thereafter, the Rr values for the three described cycles R r (1) are 84%, R r (2) 98% and R r (3) 99%. Table 3:

Abstract

L'invention concerne un procédé de production d'un copolymère à blocs multiples alternés à mémoire de forme présentant une structure constituée de macromonomères A et B qui se suivent de manière alternée. Le procédé comprend les étapes suivantes : (a) obtention du macromonomère A fonctionnalisé à ses deux extrémités par un groupe terminal nucléophile et obtention du macromonomère B fonctionnalisé à ses deux extrémités par un groupe terminal électrophile, et (b) réaction en solution du macromonomère A fonctionnalisé par un groupe terminal nucléophile avec le macromonomère B fonctionnalisé par un groupe terminal électrophile. Le rapport stœchiométrique du groupe terminal nucléophile sur le groupe terminal électrophile est ajusté de telle façon que l'écart molaire par rapport à ce rapport stœchiométrique soit au maximum de ± 8 % en moles. L'invention concerne en outre un copolymère à blocs multiples alternés qui peut être produit par le procédé revendiqué.
PCT/EP2007/059583 2006-12-08 2007-09-12 Procédé de production d'un copolymère à blocs multiples alternés à mémoire de forme WO2008068072A1 (fr)

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DE200610058755 DE102006058755A1 (de) 2006-12-08 2006-12-08 Verfahren zur Herstellung eines alternierenden Multiblockcopolymers mit Formgedächtnis
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JP2022550581A (ja) * 2019-10-01 2022-12-02 イノコア テクノロジーズ ホールディング ビー.ブイ. 生分解性の相分離した熱可塑性マルチブロックコポリマー

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