WO2009019118A1 - Process for preparing a multiblock copolymer - Google Patents

Process for preparing a multiblock copolymer Download PDF

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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
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PCT/EP2008/059394
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German (de)
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Jens Boden
Monique Hannemann
Michael Zierke
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Gkss-Forschungszentrum Geesthacht Gmbh
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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
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/73Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269Lactones
    • 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
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/721Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/12Powdering or granulating
    • C08J3/14Powdering or granulating by precipitation from solutions
    • 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
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes

Abstract

The invention relates to a process for preparing a multiblock copolymer which is composed of at least two different oligoester, oligoether and/or oligoetherester blocks, comprising the steps of: (a) providing at least two different a,w-functionalized macromonomers from the group of the oligoesters, oligoethers and/or oligoetheresters, (b) coupling the a,w-functionalized macromonomers by reacting with an aliphatic diisocyanate as a coupling reagent, preferably with HDI, in a high-boiling halogen-free solvent or solvent mixture and (c) working up the multiblock copolymer from the reaction mixture, especially by a combined precipitation/freeze-drying process, wherein, in a first step, the multiblock copolymer is precipitated by lowering the temperature and, in a second step, the solvent or solvent mixture is drawn off.

Description

A process for the preparation of a multiblock copolymer

The invention relates to a method for producing a multiblock copolymer which is composed of at least two different oligoester, oligoether and / or Oligoetherester blocks. In this case, the multi-block copolymer preferably has shape memory properties, which means that it is able to after an appropriate programming of a permanent shape to store at least one temporary shape in the "shape memory" and restore.

In the prior art are known so-called shape memory polymers or SMPs (shape memory polymers), which show when induced by an appropriate stimulus a transition in shape from a temporary shape into a permanent shape corresponding to a previous programming. Most commonly, this shape memory effect is thermally stimulated, that is, when heating the polymer material over the defined switching temperature driven by entropic elasticity provision takes place. Shape memory polymers are usually polymer networks where chemical (covalent) or physical (non-covalent) crosslinks determine the permanent shape. The programming is done by above the transition temperature a phase formed by a switching segment (= switching phase) the polymer material is deformed and then cooled while maintaining the deformation forces below this temperature, in order to fix the temporary shape. Reheating above the switching temperature leads to a phase transition and restoration of the original permanent shape. (Since the switching temperature T sw in contrast to the transition temperature Tt r a n s depends on the mechanical motion that defines the macroscopic shape change, both temperatures may be slightly different from each other.)

Shape memory polymers are often multi-block copolymers, which are mostly of two thermodynamically incompatible segments (macromonomers A and B) are constructed. The blocks A and B must each have a minimum molecular weight and a minimum portion, so that a phase separation of the blocks is ensured in the polymer. Multiblock form of physical crosslinks. The responsible for this phase is referred to as hard segment, and has the highest thermal transition temperature in the system. The phase with the next lowest thermal transition temperature is the switch segment determining phase and for switching the thermally induced shape memory effect with the switching temperature corresponding substantially to their transition temperature, in charge.

The chemical structure of multiblock copolymers is generally characterized by a random sequence of the macromonomers A and B. In contrast, (strictly) alternating multi-block copolymers can be distinguished, which are characterized by an alternating sequence of blocks A and B, and consequently the structure - (AB) n - have.

Multi-block copolymers are prepared by polyaddition or polycondensation of the macromonomers A and B.

Teng et al. (. J. Polymer Sci 42, 2004, 5045-53) discloses a multiblock copolymer of poly (ε-caprolactone) - (L-lactide) blocks and poly constructed. The polymer is made from the PCL Diisocynat (α, ω-macrodiisocyanate) and the PLLA-diol (α, ω-macrodiol). The coupling reaction of end-functionalized macromonomers takes place from the melt.

In US 6,388,043 B1 (EP 1062278 A) and US 6,160,084 B (EP 156,487 A) block will be described copolymers consisting of at least two different segments (blocks) are built and at least two temporary shapes can save "shape memory" in their , In the particular embodiment PDS macromonomers (copolymer of p-dioxane-2-one and ethylene glycol monomers) and poly (ε-caprolactone) - linked macromonomers (PCL). The coupling reaction for preparing the multi-block copolymers is carried out by reaction of end-functionalized macromonomers on both sides, namely the α, ω-macrodiols with a low molecular weight diisocyanate as a coupling reagent, namely the Strukturisomerengemisch 2.2 (4), 4-trimethylhexane-1, 6- diisoeyanat (TMDI ) in 1, 2-dichloroethane at 80 0 C, through a urethane (-NH-CO 2 -). The workup of the PDS / PCL multiblock copolymer is carried out by precipitation with hexane. An analogous method for the preparation of a PCL / PPDO-multiblock copolymer with poly (ε- caprolactone) - and poly (p-dioxanone) segments from the corresponding diols using TMDI as a coupling reagent in dichloroethane is known from WO 03/088818 A1.

DE 102 17 350 C1 describes an analogous process for the preparation of PCL / PPDL multi-block copolymers with poly (ε-caprolactone) - and poly (pentadecalactone) segments using TMDI in dichloroethane.

From DE 103 16 573 A1 multi-block copolymers are known which are made of PPDO or PCL as the soft segment and poly (ε-caprolactone-glycolide) (CG) or poly (alkylenadipinat) (AD) assembled as a hard segment. The multi-block copolymers are prepared from the corresponding macrodiols with TMDI is the link unit in dichloroethane.

In summary it can be stated that the known preparation processes for AB multiblock copolymers, in particular from hydrolytically degradable Polyetherestertyp, usually by coupling of the α, ω-macrodiols having number average molecular weights below 10,000 g / mol with the isomer 2,2 (4), 4- trimethylhexane-1, 6-diisocyanate (TMDI) in 1, 2-dichloroethane is carried out. The syntheses find so far held only on a laboratory scale with product quantities of a few 100 g. The known methods involve various problems and not likely to be transferred to a larger production scale easily, such as in the small pilot plant scale. Disadvantages are firstly the long reaction times of the coupling reaction of the macromonomers, due to the use of chlorinated solvents and moderately reactive diisocyanates as a coupling reagent. Even using tin-organic catalysts for catalyzing the reaction times can be several weeks to complete conversion. Due to the long reaction times very high polydispersities contact (ratio of weight average to number average molecular weights) of the product polymers with values ​​above 10. Furthermore, the influence of undesirable side reactions increases, particularly of cross-links, which are the material useless for further processing thereof in the solution or melt to let. In the case of poly (p-dioxanone) based multiblock copolymers can occur in the product amplified to a depolymerization of the PPDO blocks and therefore to the appearance of p-dioxanone. All this leads to the exclusion rates of up to 70%, which means that the products of two of three approaches do not meet the minimum requirements. These problems increase with increasing molecular weights of the product polymers, so far only number-average molecular weights M n were realized below 30,000 g / mol, as a rule, although higher weights due to more favorable material properties, in particular with regard to the shape memory effect, are generally desirable.

Moreover, the use of aggressive chlorinated solvent holds a higher corrosion problem on the parts of the plant and requires the use of resistant wetted materials such as glass, ceramic or PTFE, making it difficult to transfer the method in larger scale, such as small pilot plant scales. In addition, halogenated solvents are associated with a significant hazard to health and safety, especially in a scale-up. In order to keep the corrosion problem and the risk within limits, high investment costs are required in accordance with corrosion-resistant and safe investments.

Finally, applied in the prior art method of working up the felling of the highly dilute polymer solution requires the use of very large amounts of the precipitant and large vessels, which also precludes a scale-up. For example, required for a product amount of 1 kg polymer solid precipitant move in cubic meters range and require as containers 2-3 t- mixer.

Therefore, the present invention has the object of providing a method for the preparation of multiblock copolymers, in particular on the basis of hydrolytically degradable polyetherester available, which allows the synthesis of high molecular weight polymers with shape memory properties while reducing the expulsion rate. The method should also allow for scaling (scale-up) in the small pilot plant scale in particular.

This object is achieved by a method having the features of claim 1. The inventive method for preparing a hydrolytically degradable Multiblockco- polymer which is composed Goethe rester blocks of at least two different oligoester, oligoether and / or ON, comprising the steps of: a) providing at least two different α, ω-functionalized macromonomers of the group of the oligoester, oligoether and / or Oligoetherester, in particular α, ω-macrodiols, b) coupling of the α, ω-functionalized macromonomers by reaction with an aliphatic diisocyanate as a coupling reagent in a high-boiling halogen-free solvent or solvent mixture and c) workup the multiblock copolymer from the reaction mixture, wherein, in a first step, the precipitation of the multiblock copolymer by lowering the temperature, and the solvent or solvent mixture is withdrawn in a second step.

By the use of halogen-free high-boiling solvents for the coupling of the two macromonomers is first achieved that the harmful potential of the chlorinated solvents used in the prior art are largely eliminated. In addition, halogen-free solvents have a significantly lower corrosion potential, so that equipment can be used which are customary in the laboratory and small pilot plant scale. Of course, the selected solvent must have a good solubility for the used macromonomers as well as the product polymer. As a suitable example, solvents such as, 1, 3- dioxolane, 1, 4-dioxane, toluene, dimethyl carbonate (dimethyl carbonate), diethyl carbonate (diethyl carbonate) or mixtures of these proven. Be understood solvents or solvent mixtures in the context of the present application, which have a boiling point of at least 90 0 C as a high-boiling. This allows the implementation of the coupling reaction at temperatures above 80 0 C, especially at 85 0 C to give a corresponding acceleration of the reaction can be achieved. Solvents or their mixtures are preferably used which have a boiling point of at least 100 0 C. It was also surprisingly found that halogen-free solvent to halogenated solvents such as 1, 2-dichloroethane, lead to an acceleration of the reaction. In this way, undesired side reactions can be avoided and low polydispersities are obtained. In addition, in particular chlorine-containing cleavage of choir or phosgene, in contrast to halogen-containing solvents, solvents, excluded, which also lead to undesirable side reactions, for example due to peroxide formation. To further accelerate the coupling reaction as possible such diisocyanates are used as coupling reagent having a high reactivity. In particular, an aliphatic diisocyanate is used which is selected from the group consisting of 1, 6- hexane diisocyanate (hexamethylene diisocyanate, HDI), 2,2,4-trimethyl hexane-1, 6-diisocyanate, 2,4,4-trimethylhexane-1, 6-diisocyanate or a mixture of these. Of the diisocyanates mentioned 6-hexane diisocyanate (HDI) is preferably 1 was used, showing opposite TMDI an unexpected reactivity, the coupling reaction of the functionalized macromonomers, which is reflected in a higher space-time yield and hence in significantly shorter reaction times. Thus, the same conversion was found as after about 8 weeks with TMDI at otherwise identical molecular parameters in a test mixture with HDI to a reaction time of only 3 days. Due to the much shorter response times when using HDI the exclusion ratio was due to the reduced occurrence of side reactions to TMDI of 70% (after 8 weeks), to below 1% are lowered (after 3 days) (see FIG. Embodiments). A further advantage of HDI over other coupling reagents that its biocompatibility in the polymer product due to the lack of aromatic structures in the HDI molecule. This aspect is particularly important for biological and medical applications of the multiblock copolymer of interest.

By use of reactive isocyanates, in particular of 1, 6-hexane diisocyanate (HDI), in a combination of high boiling, halogen-free solvents, the reaction time of the coupling step can thus be reduced to a few days.

According to the invention the preparation of the product polymer from the reaction mixture by a combined precipitation freeze-drying method, wherein, in a first step, the precipitation of the multiblock copolymer by lowering the temperature, and the solvent or solvent mixture is withdrawn in a second step. refer to the (still hot) reaction solution is preferably introduced into a vessel at very low temperatures, in particular in a template of inexpensive liquid nitrogen, whereby there is a sudden precipitation and freezing of the product polymer, which is obtained in particular as a fine granulate. In this case, an intense stirring in the nitrogen template is preferably carried out, whereby a very fine granulation of the multiblock copolymer is obtained. Subsequently, the frozen granulate lat / solvent mixture is subjected to a vacuum so that the solvent is removed. Preferably, this step is carried out at such low temperatures that the solvent sublimes, that is, directly from the fixed (frozen) state of aggregation into the gaseous passes. Compared with the usual in the prior art the precipitation of the polymer by addition of large amounts of suitable solvents ( "non-solvent") as a precipitant, in which the product polymer is not soluble, for example hexane, to significantly reduce the necessary amounts of solvent in the inventive process. the work-up is preferably carried out even without the addition of a precipitant.

Following a slightly modified procedure, the precipitation of the Multiblockcopoly- mers is accomplished by the initially still hot reaction solution, a solvent or solvent mixture "substoichiometric" added, in which the polymer is substantially insoluble, wherein the amount used, however, well below the prior art usual amounts is. However, this is not coming due to the raised temperature a complete precipitation of the polymer, but usually only a slight turbidity of the reaction solution, that is to form a suspension. As suitable precipitating agent (non-solvent) have been shown, for example, n-butyl acetate, tert-butyl acetate, dibutyl ether or methanol in this context. the actual precipitation made by lowering the temperature - below - as described above. The above-described procedure is particularly advantageous when the subsequent removal of the solvent can not be continuously performed in the frozen state or intended, as the added non-solvent prevents sticking of the molten granules, and thus a fine-grained distribution of the multiblock copolymer can be obtained.

A further advantage of the inventive process is the fact that can be displayed due to the shorter reaction time and the associated reduction of undesired side reactions always multiblock copolymers with higher molecular weights compared to the prior art. In this case, polymers having number average molecular weights are preferred M n of at least 30,000 g / mol, preferably made of at least 35,000 g / mol. Preferably, the macromonomers are used, the n has a number average molecular weight M of at most 10,000 g / mol.

Preferred are macromonomers selected from the group comprising poly (p-dioxanone) (PPDO), poly (pentadecalactone) (PPDL), poly (ε-caprolactone) (PCL), poly (D, L-lactide), poly (L- lactide, poly (glycolic acid) and poly (ethylene glycol).

A further acceleration of the process can be achieved by performing the coupling reaction in the presence of a suitable organotin catalyst, especially dibutyltin dilaurate or other.

Further advantageous embodiments of the invention are subject of the remaining claims.

The invention is explained in more detail below with reference to embodiments of advantageous executions of the method.

Example 1: Preparation of HDI-coupled PPDO / PCL multiblock copolymer

500 g of poly (p-dioxanone) diol having a number average molecular weight of 5,000 g / mol (PPDO 5k) and 500 g of poly (ε-caprolactone) diol having a number average molecular weight of 2,000 g / mol (PCL 2k, CAPA ® 2205 ) both in solid form (powder or wax) as well as 1, 5, I 1, 3-dioxolane and 1, 5 l of toluene (both previously at least 24 h dried over a freshly calcined molecular sieve 4 Å at room temperature) were placed in a 4I glass reactor (Rettberg) filled with flat bottom and tempering at 85 0 C. bath temperature of the thermostat. The reactor was equipped with a helical (1/2 beba hand mixer type B050 stainless steel), a stirring motor (Heidolph), a chiller (15 0 C, Julabo), a circulator (85 0 C, MW Julabo, MC 4 or MC 6 ), an intensive cooler made of glass (Schott) and a mechanical seal (HWS) with Doppelkardanwelle. By gently lifting the stirrer speed of 0 to 150 U / min at 85 0 C. bath temperature the macrodiols were dissolved. After dissolution of the macrodiols the addition of 150 .mu.l of dibutyltin dilaurate and after another 15 min by addition of about 55 ml hexamethylene diisocyanate HDI (100% of theory..) Is carried out. The addition of HDI marks the beginning of the reaction. For the monitoring of the reaction by means of in-process control sample volumes were taken at regular intervals of 0.5 g to track the molecular weight distribution and the qualitative NCO content by single determination. It was geometry by FTIR spectrometer at v = 2270 cm "1 (NCO bands) controls whether residual NCO of the HDI was still present. The determination of the molecular weights was performed by GPC The following targets for molecular weights as criteria for were. the termination of the reaction given:

Lower limit M n:> 30,000 g / mol lower limit M w:> 130,000 g / mol lower limit M p:> 70,000 g / mol

Optimum value M n:> 35,000 g / mol

Optimal M w:> 150,000 g / mol

Optimum value M p:> 85,000 g / mol

If the limits of the molecular weights were not yet achieved, but at the same time no NCO was no longer detectable in the FTIR, 10 ml, 5 ml and 1 ml were further amounts HDI, typically in the order metered by means of a disposable syringe.

The reaction was upon exceeding at least one of the above mentioned molecular weight limits ended (here after exactly 3 days) by added to 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 hours at 85 0 C, with a milky haze of the hot reaction solution occurred, that is, began the precipitation of the polymer product. The 1, 8-octanediol served while the complete reaction of any unreacted isocyanate groups. The suspension was also pumped from PP at 85 0 C over a (valveless) wobble piston metering pump from the reaction vessel in a liquid nitrogen filled with 5-liter plastic beaker. The polymer solution should in this case have a consistency at the selected dosing rate (0,2 - 0,5 l / min) permits dropwise addition of the solution into the precipitant. In the liquid nitrogen, the quantitative precipitation of the polymer then took place, which was obtained as immediately frozen granules and was further reduced in size by intensive stirring with a paint disperser (IKA). The resulting granules were allowed to separate from the liquid nitrogen through Abdekanntieren and drained on a filter bag made of PP non-woven. Subsequently, the frozen granules were dried in photo-shells made of PP in a freeze-drying process to constant weight.

Following the drying, the total yield was determined by weighing. Furthermore, samples for the analysis and characterization measurements were taken by means of DSC and train-strain.

Example 2: Preparation of TMDI-coupled PPDO / PCL multiblock copolymer

It was prepared as described in Example 1, a reaction PPDO / PCL multiblock copolymer, but using as a coupling reagent instead of TMDI HDI under otherwise identical molecular parameters. The reaction time was about 8 weeks for the molecular weight above criteria were met and the coupling reaction was stopped.

Example 3: Preparation of HDI-coupled PPDL / PCL multiblock copolymer

Using 400 g of poly (pentadecalactone) -diol having a number average molecular weight of 3,000 g / mol (PPDL 3k) and 600 g of poly (ε-caprolactone) diol having a number average molecular weight of 3,000 g / mol (PCL 3k CAPA ® 2304) was prepared PPDL / PCL multiblock copolymer according to the process described in example 1 reaction using HDI as a coupling reagent. The reaction time was 3 days until the molecular weight above criteria were met and the coupling reaction was stopped.

Example 4: Preparation of TMDI-coupled PPDL / PCL multiblock copolymer

It was prepared according to Example 3, a PPDL / PCL multiblock copolymer, but using as a coupling reagent TMDI instead of HDI as a coupling reagent under otherwise identical molecular parameters. The reaction time was about 8 weeks for the molecular weight above criteria were met and the coupling reaction was stopped. Chemical, thermal and mechanical properties of multi-block copolymers

In the following tables, molecular weight, thermal and mechanical properties of the PPDO / PCL multiblock copolymers are listed, which (according to Examples 1 and 2 by coupling with 1, 6-hexane diisocyanate (hexamethylene diisocyanate, HDI) (Table 1) or with 2.2 4), 4-trimethylhexane-1, 6-diisocyanate (TMDI) (Table 2) were prepared, and the PPDL / PCL multiblock copolymers, which (according to examples 3 and 4, which were prepared by coupling with HDI or TMDI Table 3) were prepared. The molecular, thermal and mechanical properties of the polymers meet the conditions for functionalization of the multiblock copolymers as shape memory materials. It has been shown in particular that very high molecular weights with relatively low polydispersity PD capacities were obtained.

Due to significantly shorter reaction times the reaction mixtures with HDI as a coupling reagent to the reaction approaches with TMDI (3 days in Examples 1 and 3 to 8 weeks in Examples 2 and 4), the reject rate was due to the increased occurrence of side reactions at the TMDI approaches at about 70% compared to less than 1% in HDI insertions. The product polymers listed in the tables were each the result of approaches that met the minimum quality requirements.

Table 1: HDI coupled PPDO / PCL multiblock

Figure imgf000012_0001
Figure imgf000013_0001

Table 2: TMDI coupled PPDO / PCL multiblock

Figure imgf000013_0002
Figure imgf000014_0001

Figure imgf000014_0002

Claims

1. A process for the preparation of a multiblock copolymer which is composed of at least two different oligoester, oligoether and / or Oligoetherester blocks, comprising the steps of:
(A) providing at least two different α, ω-functionalized macromonomers of the group of the oligoester, oligoether and / or Oligoetherester,
(B) coupling of the α, ω-functionalized macromonomers by reaction with an aliphatic diisocyanate as a coupling reagent in a high-boiling halogen-free solvent or solvent mixture and
(C) working up of the multiblock copolymer from the reaction mixture by a combined precipitation freeze-drying method, wherein, in a first step, the precipitation of the multiblock copolymer by lowering the temperature, and the solvent or solvent mixture is withdrawn in a second step.
2. The method according to claim 1, characterized in that the solvent or solvent mixture has a boiling point of at least 90 0 C, preferably of at least 100 0 C, has.
3. A method according to any one of claims 1 or 2, characterized in that the solvent used is 1, 3-dioxolane, 1, 4-dioxane, toluene, dimethyl carbonate, diethyl carbonate or a mixture of these.
4. The method according to any one of the preceding claims, characterized in that the aliphatic diisocyanate is selected from the group comprising 1, 6-hexanediamine diisocyanate (HDI), 2,2,4-trimethyl hexane-1, 6-diisocyanate, 2, 4,4-trimethyl hexane-1, 6- diisocyanate, or a mixture of these, preferably 1, 6-hexane diisocyanate.
5. The method according to any one of the preceding claims, characterized in that for lowering the temperature, the reaction solution is passed into a template from liquid nitrogen.
6. The method according to any one of the preceding claims, characterized in that the removal by sublimation of the frozen solvent takes place under vacuum.
7. The method according to any one of the preceding claims, characterized in that the reaction solution is added before the reduction in temperature, a solvent or solvent mixture in deficit, in which the polymer is substantially insoluble.
8. The method according to any one of the preceding claims, characterized in that said multiblock copolymer has a number average molecular weight M n of at least 30,000 g / mol, in particular at least 35,000 g / mol.
9. The method according to any one of the preceding claims, characterized in that the macromonomers are selected from the group comprising poly (p-dioxanone) (PPDO), poly (pentadecalactone) (PPDL), poly (ε-caprolactone) (PCL)), poly (D, L-lactide), poly (L-lactide, poly (glycolic acid) and poly (ethylene glycol).
10. The method according to any one of the preceding claims, characterized in that the macromonomers have a number average molecular weight M n of at most 10,000 g / mol.
1 1. A method according to any one of the preceding claims, characterized in that the coupling reaction is carried out in the presence of an organotin catalyst, in particular dibutyltin dilaurate.
12. The method according to any one of the preceding claims, characterized in that α as α, ω-functionalized macromonomers, ω-macrodiols can be used.
PCT/EP2008/059394 2007-08-03 2008-07-17 Process for preparing a multiblock copolymer WO2009019118A1 (en)

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