(19)
(11)EP 3 502 161 A1

(12)EUROPEAN PATENT APPLICATION

(43)Date of publication:
26.06.2019 Bulletin 2019/26

(21)Application number: 17210556.1

(22)Date of filing:  23.12.2017
(51)International Patent Classification (IPC): 
C08G 63/08(2006.01)
C08G 63/84(2006.01)
(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
Designated Extension States:
BA ME
Designated Validation States:
MA MD TN

(71)Applicant: Technische Universität München
80333 München (DE)

(72)Inventors:
  • ADAMS, Friederike
    80798 München (DE)
  • RIEGER, Bernhard
    89275 Elchingen (DE)

(74)Representative: Leißler-Gerstl, Gabriele 
Hoefer & Partner Patentanwälte mbB Pilgersheimer Strasse 20
81543 München
81543 München (DE)

  


(54)PROCESS FOR POLYMERIZING SS-BUTYROLACTONE


(57) A process for polymerizing ß-butyrolactone is disclosed comprising contacting racemic ß-butyrolactone or an enantiomer thereof with a catalyst/initiator system which comprises a rare earth metal, a chiral ligand, at least one nucleophilic ligand, at least one solvent ligand, and optionally an alkali based co-catalyst.




Description


[0001] The present invention is concerned with a process for polymerizing racemic β-butyrolactone. to obtain polymers with high isotacticity, and with a polymer obtained with this process.

[0002] Poly(3-hydroxybutyrate) (PHB) is a biopolymer that is produced by microorganisms. In its natural form it is a strictly isotactic polyester of the monomer 3-(R)-hydroxybutyric acid. This polymer is highly valuable as it is biodegradable, is a renewable resource, has barrier properties and has convenient thermoplastic properties similar to those of polypropylene. Although natural PHB is a valuable resource, there are some properties which could be improved, in particular the thermoplastic properties. Moreover, it is desirable to provide a synthetic process for preparing these polymers.

[0003] It is known to produce PHB polymers by fermentation of glucose containing materials, i.e. food resources. From an ethical view it is not desirable to use food materials for the production of technical products. Moreover, using a fermentation process results in a polymer which is similar to the polymer produced by microorganisms, i.e. a highly isotactic (R)-polymer, and has the same disadvantages. Due to the high crystallinity of these polymers it is very brittle and has a melting temperature which is near the decomposition temperature which makes its processability impossible.

[0004] β-butyrolactone as a monomer for PHB synthesis is obtainable by a synthesis method using propylene oxide and CO2, i.e. readily available cheap products. However, this method yields racemic β-butyrolactone which consists of same amounts of (R)- and (S)- β-butyrolactone. It is desirable to be able to use racemic ß-butyrolactone for producing isotactic PHB.

[0005] Methods have been described for the synthesis of PHB polymers via a ring opening polymerization using different catalysts. Many catalysts have been developed in the past, but most of these catalysts produce only atactic or syndiotactic PHB polymers. These syndiotactic or atactic PHB polymers have inferior properties than isotactic polymers. In particular they are not biodegradable and the thermoplastic properties are not optimal.

[0006] Thus, those PHB polymer products that are presently available are either not biodegradable or have less desirable mechanical properties.

[0007] Although, it would be possible to prepare isotactic PHB polymers by using enantiomerically pure β-butyrolactone, i.e. either only the (R)-enantiomer or only the (S)-enantiomer, this option is not feasible as the separation of enantiomers is very time and cost consuming.

[0008] Thus, it is an object of the present invention to provide a process wherein racemic β-butyrolactone can be used and nevertheless an isotactic polymer can be obtained. Moreover, it was an object of the present invention to provide a process for preparing PHB polymers having improved mechanical properties but at the same time are biodegradable. Moreover, it was an object to provide a process for preparing a polymer with a predetermined percentage of isotacticity. It was another object of the present invention to provide a polymer that can be produced from monomers that are readily available and/or can be produced from cheap components. Furthermore, it was an object of the present invention to provide a polymer having barrier properties.

[0009] All these objects are obtained by using a process as defined in claim 1 and by polymers obtained by the processes described in this application.

[0010] A process for polymerizing ß-butyrolactone with an isotacticity of at least 60% is provided which comprises contacting racemic ß-butyrolactone or an enantiomer thereof with a catalyst/initiator system which comprises a rare earth metal, a chiral ligand, at least one nuceophilic ligand, at least one solvent ligand, and optionally an alkali based co-catalyst, wherein the chiral ligand is an enantiomer of a unit of formula I

wherein each Rz independently is linear or branched, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C5-C20 heteroaryl, or halogen; wherein each Ra independently is H or an alkali metal.

[0011] The catalyst/initiator system that is used in the method of the present invention is based on a rare earth metal and comprises a chiral ligand as essential part of the system.

[0012] In one embodiment the catalyst/initiator system is obtained by contacting a chiral ligand of formula I with a compound of formula II:

and optionally an alkali based co-catalyst,

wherein M is a rare earth metal,

each Rx independently is a nucleophilic ligand,

each Ry independently is a solvent ligand,

n is an integer from 1-5, such as 1-3,

m is an integer from 0-5, such as 1-3 with the proviso that n + m is an integer corresponding to the number of association/bonding sites of the rare earth metal, the upper limit of which is the number of available association/bonding sites on the rare earth metal, which is up to 9, such as 5 or 6.



[0013] In another embodiment the catalyst/initiator system is obtained by contacting a chiral ligand of formula I with a rare earth metal compound of formula III MX3(Ry)m, wherein M is a rare earth metal, Ry and m are as defined above and each X independently is halogenide, triflate, or C1-C20 alkoxide, and with a solvent, and optionally an alkali based co-catalyst, For activation the obtained complex is contacted with an alkali salt of a nucleophilic ligand (co-catalyst). When contacting these components a complex is obtained which comprises a rare earth metal atom bound/associated with the chiral ligand and with at least one nucleophilic ligand and/or solvent ligand. When this route is used, the complex can also include alkali species, for example lithium or potassium halogenides.

[0014] The catalyst/initiator system can be obtained with or without a co-catalyst. Moreover, the catalyst/initiator system of the present invention can be obtained by first preparing a rare earth metal compound of formula II, wherein the rare earth metal atom carries already at least one nucleophilic ligand and at least one solvent ligand. It is also possible to prepare the catalyst/initiator system in a one pot reaction, with or without a co-catalyst. Furthermore, after the reaction the complete catalyst/initiator system can be isolated or the reaction mixture can be used directly. In other words, the catalyst/initiator system can be either prepared in situ, i.e. the components of the system can be added to the monomer composition and the system provides the catalytic activity directly. It is also possible to prepare the catalyst/initiator system separately, isolate it and to add it to the monomer composition.

[0015] Surprisingly it has been found that when using a catalyst/initiator system as defined in claim 1 it is possible to produce PHB polymers that have a predeterminable amount of isotacticity, a predeterminable amount of imperfections and combine mechanical strength with biodegradability. Such biodegradable polymers can be used for many purposes, for example for packaging. Moreover, it has been found that these polymers still have highly desirable barrier properties, in particular have a high oxygen barrier. By introducing imperfections the mechanical properties are improved compared to natural occurring or microbial produced PHB polymers, i.e. the polymers produced with the process of the present invention have a lower melting point, are less brittle and rigid and have a higher tensile strength.

[0016] These valuable properties are obtained by using the process of the present invention, in particular by using the catalyst/initiator system as defined in claim 1.

[0017] It has been found that a catalyst/initiator system comprising a rare earth metal based compound, a chiral ligand and optionally an alkali-based co-catalyst allows to polymerize racemic β-butyrolactone to obtain isotactic PHB with either a majority of (R)-enantiomers or a majority of (S)-enantiomers. Although a racemic mixture of monomers is used, the polymer comprises only one type of enantiomers with some imperfections. These imperfections in the polymer introduced by the catalyst/initiator system of the present invention provide for the improved mechanical properties. The amount or percentage of imperfections can be controlled in the process of the present invention by parameters as disclosed below, and it should be low enough to maintain the biodegradability which is a valuable property of the polymer.

[0018] The figures further explain the subject matter of the present invention.

Fig. 1 shows a conversion per time diagram for racemic β-butyrolactone using a catalyst/initiator system of the present invention.

Fig. 2 shows 13C-NMR-spectrograms which are used to determine the microstructure of the polymer obtained with a process of the present invention. For analysis it is possible to either evaluate the carbonyl signal at 169 ppm (see Fig. 2a) or the methylene signal at 40 ppm (see Figs. 2b-d). The ratio between the isotactic part of the polymer (mm and rm) and the syndiotactic part (rr and mr) has been calculated for PHB examples in deuterated chloroform with different isotacticity ratios from 0.70 to 0.88.

Fig. 3 shows the DSC diagram for a PHB example that has been obtained using the process of the present invention. It can be seen that the melting temperature Tm is 166°C and, thus, lower than the melting point of known polymers.



[0019] The following definitions are used in the present application.

[0020] The term "rare earth metal" refers to the group as defined by IUPAC, i.e. scandium, yttrium and lanthanum and lanthanides. Specific examples of rare earth metals are yttrium and lutetium.

[0021] A "chiral ligand" refers to a unit that has an axial chirality and has at least one chiral center. Because of the axial chirality the unit can occur in at least two enantiomeric units, one of the enantiomeric units ((R)- or (S)-compound) is used for the catalyst/initiator system of the present invention.

[0022] A "solvent ligand" is a ligand that is based on a solvent, such as tetrahydrofuran, and can associate with the rare earth metal.

[0023] A "nucleophilic ligand" is a ligand that can associate with the rare earth metal because of a nucleophilic site, such as nucleophilic nitrogen or nucleophilic carbon groups. Examples are substituted amido ligands, C1-C20 alkoxides and di- or trialkyl methyl-silyl groups. Otherwise the structure of the ligand is not critical as long as it does not interfere with bonding/association of rare earth metal. Examples for a substituted amido ligand or carbon-ligand are NRbRcRd, ORb and CHRbRc, wherein each of Rb,R,c and Rd independently is H or a group selected from linear or branched, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C5-C20 heteroaryl, arylalkyl, silylalkyl, wherein the substitution can be as defined below.

[0024] The integer n+m corresponds to the coordination number or number of association/bonding sites of the rare earth metal that is the core of the catalyst. The number of available sites for association or bonding with the rare earth metal is the number that is occupied by ligands. Rare earth metals normally have a coordination number of up to 9. Thus, the sum of n and m can be an integer up to 9, such as 3, 4, or 6.

[0025] A linear or branched C1-C20-alkyl is an alkyl group having 1 to 20 carbon atoms which can be in a line or can have branches, such as a C1-C10 alkyl group, particularly a C1-C4 alkyl group. A substituted alkyl is an alkyl which is substituted with groups like OH, NH2, NHR, NR2, OH, OR, SH, SR, halogen, wherein halogen comprises chlorine, iodine, fluorine, and bromine, wherein R is C1-C4-alkyl.

[0026] C6-C20-aryl refers to an aromatic group, like benzyl, phenyl, naphthyl, biphenyl etc.

[0027] Arylalkyl refers to a C6-C20-aryl group substituted with alkyl as defined above.

[0028] Silylalkyl refers to silyl units carrying one, two or three C1-C4-alkyl groups. such as Si(alk)3, SiH(alk)2, SiH2(alk), wherein alk is C1-C4-alkyl.

[0029] Nucleophilic carbon groups are carbon comprising groups carrying 1-3 mono-, di- or trialkylsilyl units,

[0030] Alkoxide refers to an O-Alkyl group, wherein "alkyl" is a linear or branched C1-C20-alkyl, as defined above, preferably an O-C1C10 alkyl group.

[0031] C5-C20-heteroaryl refers to heteroaryl groups, i.e. aromatic groups comprising at least one heteroatom, wherein the heteroatom is selected from N, S, and O. Examples for heteroaryl are furanyl, thienyl, pyrrolyl, pyridyl, isochinolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl etc.

[0032] The terms "halogen" or "halogenide" comprise chloro, fluoro, bromo, iodo, or chloride, fluoride, bromide, iodide, respectively.

[0033] A "monomer composition" is a composition comprising at least monomers to be polymerized, i.e. ß-butyrolactone and can comprise additionally one or more solvents. If a copolymer shall be produced, the composition can comprise further monomers. As ß-butyrolactone is fluid at room temperature, it can be used as it is. The monomer can also be used in a solvent such as toluene.

[0034] For polymerizing β-butyrolactone having desirable properties a specific catalyst/initiator system is used. In general the polymerization can be summarized as follows:



[0035] The catalyst/initiator system of the present invention comprises a rare earth metal based catalyst and a chiral ligand wherein the rare earth metal is in complex with the chiral ligand which occupies 4 association/bonding sites, at least some of the remaining association/bonding sites of the rare earth metal are occupied by ligands, i.e. nucleophilic ligands and/or solvent ligands, and/or anions like halogenide, triflate, or C1-C20 alkoxide up to the coordination number.

[0036] The catalyst/initiator system of the present invention can be prepared by reacting a chiral ligand and a rare earth metal based compound. The chiral ligand is an important part of the system, as it provides for the incorporation of one type of enantiomer of β-butyrolactone in the polymer chain. The chiral ligand used according to the present invention is an enantiomer of a compound of formula I:

wherein Ra and Rz as defined above.

[0037] This compound is a substituted binaphthol, examples of which are well-known in the art under the name BINOL-box. Methods for producing these compounds are well-known to the skilled person and have been published in the literature, for example Kodama, H., Ito, J., Hori, K., Ohta, T., & Furukawa, I. (2000). Lanthanide-catalyzed asymmetric 1, 3-dipolar cycloaddition of nitrones to alkenes using 3, 3'-bis (2-oxazolyl)-1, 1'-bi-2-naphthol (BINOL-Box) ligands. Journal of Organometallic Chemistry, 603(1), 6-12. The core of this compound is a binaphthyl group, i.e. two naphthyl groups connected by a 1-1 bond. Both carry a hydroxy group in position 2 and a heterocyclic group in position 3. This part of the core provides for the complex with the rare earth metal which is necessary for the catalytic activity. The two heterocyclic groups carry a group Rz at position 4 or 5, preferably at position 4. Rz can be substituted or unsubstituted alkyl, substituted or unsubstituted aryl, heteroaryl, or halogen. This group is not critical as long as it does not interfere with or affect the bonding of the rare earth metal to the four specific association sites of this unit. Rz for example can be linear or branched alkyl, such as methyl, ethyl, n-propyl, n-butyl, isobutyl or isopropyl. The alkyl chain can be substituted by groups like hydroxy, amino, halogen. Rz can also be an aryl group like phenyl or naphthyl or a heteroaryl group. Rz can be bound to the oxazolyl group in two configurations. For the chiral ligand of the present invention it is preferred that both groups Rz have the same configuration, i.e. are both (R) or both (S). Therefore, when it is referred to the chiral ligand the term "(R)(R)-BINOL box" means that the two naphthyl rings are in (R) configuration and both Rz groups are in (R) configuration. An (S)(R)-BINOL box refers to a compound wherein the two naphthyl rings are in (S) configuration and both groups Rz are in (R) configuration etc.

[0038] The chiral ligand as defined above and in the claims is reacted/has been reacted with a rare earth metal based compound to obtain the system that provides activity as polymerization catalyst. In the catalyst/initiator complex in its active form the rare earth metal binds/coordinates with the chiral ligand via the two ORa groups and via the nitrogen atoms of the heteroaryl rings.

[0039] Producing such complexes is known to the skilled person. There are different approaches to obtain such complexes. The active catalyst/initiator system, which activates a monomer for polymerization is a complex which is formed by contacting the chiral ligand with the rare earth metal based compound. This complex can be obtained either by separate reaction and isolation of the complex or in situ.

[0040] In one approach the chiral ligand is contacted with a rare earth metal compound according to formula II. It has been found that a compound of formula II which comprises a nucleophilic ligand is active enough to combine with the OH groups of the chiral ligand (amine elimination reaction), i.e. with Ra being H. In this approach no co-catalyst is necessary, although it can be used. Thus, in a variation of this method, an alkali compound like n-butyl lithium can be used to activate one or both OH groups of the chiral ligand for bonding. The alkali metal of the deprotonating agent in this approach can become part of the catalyst/initiator complex.

[0041] It is assumed without being bound by theory that some of the ligands of the rare earth metal compound of formula II are replaced by bonding/association with the chiral ligand but some remain. It is assumed that at least one nucleophilic ligand and at least one solvent ligand are necessary for the activity of the catalyst/initiator complex of the present invention. These ligands can be provided by using a rare earth metal compound of formula II for preparing the complex. As outlined before, in the complex the rare earth metal in addition to the association with the chiral ligand associates with or carries further ligand(s), at least one nucleophilic ligand and/or at least one solvent ligand, to obtain a coordination number of 6, The solvent ligand can be provided by the rare earth metal compound of formula II or can be attached from the reaction mixture, when said mixture comprises a solvent.

[0042] The solvent ligand is a solvent molecule, such as a molecule from the solvent used for dissolving the rare earth metal salt and/or the system or which is present in a compound of formula II as Ry. A solvent ligand can be exchanged easily when contacted with a monomer. It can be any solvent that is used for this type of compounds and is able to coordinate to metal centers, such as tetrahydrofuran (THF), 1,4-dioxane or diethylether. Other solvents can also be used as long as they have no active proton, protic solvents like alcohols or acids are not suitable. Preferred are solvents that have oxygen but no active proton like dioxane, THF or ether.

[0043] The nucleophilic ligand can be a nitrogen and/or carbon and/or oxygen comprising group, for example a substituted amino or amido group, such as a dialkylamido, diarylamido or disilylalkylamido group carrying 1-3 trialkylsilyl units, such as N(SiH(alk)2)2 or N(Si(alk)3)2,. Examples for carbon comprising nucleophilic groups are groups carrying 1-3 mono-, di- or trialkylsilyl units, such as CH2Si(alk)3, CH(Si(alk)3)2, CH(SiH(alk)2)2, C(Si(alk)3)3, wherein alk is C1-C4-alkyl.

[0044] Compounds that are well suited for this approach are yttrium compounds having 3 nucleophilic ligands and up to 3 solvent ligands. The number of ligands depends on the number of available association/binding sites of the metal. A useful rare earth compound is the following:



[0045] Without being bound by theory it is assumed that when contacting this type of rare earth metal compound with a chiral ligand some of the ligands are replaced by bonds to the chiral ligand, whereas some ligands remain which then provide for the catalytic activity for polymerization.



[0046] The catalyst/initiator complex obtained allows to polymerize ß-butyrolactone at room temperature (about 20°C) and yields isotactic PHB with a Pm between about 0.6 and about 0.9, such as 0.7 to about 0.88, depending on the reaction conditions, the used solvents and the chirality of the chiral ligand with some imperfections.

[0047] It is assumed that when contacting the chiral ligand with a rare earth metal compound like the yttrium compound shown above, the core atom associates with the two hydroxy groups of the binaphthyl and with the two nitrogen atoms of the oxazole rings. This complex can be isolated by washing with an apolar solvent like pentane or diethylether. The catalyst/initiator system is very active and results in a high polymerization rate.

[0048] The catalyst/initiator complex can also be used without isolation as can be seen in scheme 2:



[0049] The reaction is carried out in a solvent like THF, 1,4-dioxane, diethylether or another solvent. The reactants are reacted at room temperature for some time, the reaction time is not critical, it can be a few minutes up to an hour, for example 10 to 40 minutes, but also longer, such as overnight. If an in situ catalyst/initiator system is used the reagents can be reacted for some minutes up to a day or more, such as 0.5 to 24 hours or 1 to 12 hours, for example overnight.

[0050] As an example the active catalyst/initiator system is prepared in situ, the reaction mixture comprising the catalyst/initiator complex is used directly for polymerization of ß-butyrolactone. The polymerization can be carried out at room temperature (about 20°C). PHB is obtained with an isotacticity/Pm of 0.70. Thus, when using an isolated catalyst/initiator complex the number of imperfections is lower than when using catalyst/initiator complex without isolation. This shows that one measure to control isotacticiy of the polymer is to control the purity of the catalyst/initiator complex - the higher the purity of the catalyst/initiator complex the lower the amount of imperfections and the higher the isotacticity.

[0051] In another embodiment the active catalyst/initiator system is prepared by deprotonating a chiral ligand of formula I and reacting it with a rare earth metal compound like yttrium chloride as rare earth metal compound in the presence of an oxygen containing solvent which can serve as a solvent ligand Ry. Thereafter, the complex obtained is reacted with a co-catalyst and subsequently polymerization is performed as can be seen in Scheme 3

In this case the chiral ligand is activated by a deprotonating agent like nBuLi and, thus, makes available the binding sites for the rare earth metal. Furthermore, the rare earth metal compound is added as rare earth metal salt, such as halogenide. After isolation the compound is activated with co-catalyst lithium bis(dimethyl)silyl amide (LIBDSA) to provide at least one nucleophilic ligand. The catalyst/initiator complex obtained is used for polymerization, it is active at room temperature and yields PHB with high isotacticity of 0.79. It has been found that the use of a co-catalyst reduces the number of imperfections and increases the degree of isotacticity. At the same time polymerization speed is reduced.

[0052] Without being bound by theory the structure of one embodiment of a catalyst/initiator complex of the present invention can be depicted as follows:



[0053] A further embodiment is shown in Scheme 4, where a deprotonating agent is used to deprotonate the OH groups of the chiral ligand and the activated chiral ligand then is reacted with a rare earth metal compound of formula II to form a catalyst/initiator complex of the present invention. This catalyst/initiator complex can be isolated by using a solvent like pentane. It is also possible to use the reaction mixture without isolation.



[0054] The catalyst/initiator system of the present invention that can be obtained as outlined above provides for stereospecific polymerization because of its structural composition. The catalyst/initiator system of the present invention comprises as essential part a chiral ligand, a 1,1'-binaphthol based ligand which is referred to as chiral ligand. As outlined before, this ligand has at least two chiral centers, the chirality of the binaphthol, and the position of the two substituents Rz. Thus, the chiral ligand can be in (R)(R)-, (S)(R)-, (R)(S)- and (S)(S)-form. This form has an influence on the microstructure which is obtained for the polymer. It is easy to find out which monomer is preferred by a chosen catalyst/initiator complex by some routine tests.

[0055] For preparing the catalyst/initiator system of the present invention either the components can be reacted separately, isolated and then used in isolated form or the components can be mixed and the mixture can be used as it is without isolation.

[0056] It has been found that the purer the catalyst system is, the more selective it is, i.e. the higher the amount of isotacticity is. With the isolated catalyst/initiator system an isotacticity rate of up to about 0.9, such as 0.88 can be obtained. Thus, the degree of isotacticity can be controlled by using an isolated versus an in situ catalyst/initiator complex.

[0057] Critical for the catalyst/initiator system of the present invention is that it comprises a chiral ligand, a rare earth metal atom as core or catalytic atom, at least one nucleophilic ligand and at least one solvent ligand which can be exchanged for a monomer for the polymerization reaction.

[0058] The catalyst/initiator system of the present invention selectively polymerizes one enantiomer of β-butyrolactone, either (R)-β-butyrolactone or (S)-β-butyrolactone, with some imperfections, which is desirable.

[0059] The polymerization reaction takes place in solution. The β-butyrolactone can be used as solvent or a solvent that can dissolve the reactants can be used. Examples for useful solvents are toluene, THF, 1,4-dioxane and diethylether. It is also possible to run the polymerization without a solvent because the monomer, i.e. β-butyrolactone, can serve as solvent itself. As, however, the system becomes more viscous when the polymer chains become longer, a solvent is advisable if high molecular weights are considered.

[0060] It was found that the slower the polymerization reaction is the more exact the monomers are added to the polymer chain so that the isotacticity becomes higher. On the other hand, when speed is increased, for example by increasing the temperature of the reaction the polymerization rate becomes faster and the number of imperfections increases. In this case isotacticity decreases.

[0061] Furthermore, it was found that the solvent ligand of the catalyst/initiator complex or, in case of an in situ catalyst/initiator complex, the solvent used, has an influence on isotacticity. Without being bound by theory it is assumed that this is due to the fact that the solvent ligand in the catalyst/initiator system has an influence on the type of monomers that is taken up and added to the polymer chain. In this regard it was found that dichloromethane is a good solvent to obtain an isotacticity in the desired range, i.e. 60 to 80% isotacticity. Toluene is a solvent which increases the speed of polymerization. The solubility is not as high as with dichloromethane so that polymer chains precipitate when they become too long. Therefore, toluene can be used as solvent if polymers with a medium to low molecular weight are desired. Furthermore, THF is a solvent that coordinates very well with the rare earth metal and can be added as ligand. Thereby, catalyst activity and polymerization speed can be decreased, which has an influence on isotacticity, it is lower.

[0062] Any factor, that has an influence on the the polymerization rate can also influence isotacticity. Therefore, the ratio of monomer and catalyst can also influence isotacticity.

[0063] By controlling the isotacticity of the polymer built with the catalyst/initiator system of the present invention and by controlling the number of imperfections, it is possible to fine tune the properties of the polymer that is obtained. Thereby the mechanical properties of the polymer can be optimized. By selecting the temperature, the solvent, the configuration of the chiral ligand and the ligands of the rare earth metal based catalyst it is possible to produce PHBs with different microstructures. This is particularly valuable.

[0064] Another aspect of the present invention are polymers that have been obtained with a method as described. These polymers are superior to known polymers as they have a high enough isotacticity to be biodegradable but have a controllable number of imperfections to allow for superior mechanical properties. A desirable range of isotacticity is 50 to 90%, preferably 55 to 85 %, and in particular 60 to 80%.

[0065] The polymers obtained with the method of the present invention have been analyzed with methods as described in the following. To find the best suited catalyst/initiator system for a specific polymer experiments can be carried out as is explained in detail below.

[0066] NMR kinetic experiments can be carried out to determine catalyst activities as is known to the skilled person. For this purpose, conversions from NMR values are recorded in a conversion or turnover per time diagram. From the conversion rates it can be seen that either the S-monomer or the R-monomer is consumed as about 50% of the monomer is consumed and about 50% of the monomer remain, this shows that only one of the enantiomers of the β-butyrolactone has been consumed, by analyzing which of both enantiomers remains in solution it can be analyzed which preference the system has. Fig. 1 shows a conversion per time diagram for racemic β-butyrolactone using a catalyst/initiator system as described in detail with reference to the schemes. From the curve it can be seen that only one enantiomer was converted. To determine if a system is specific for R- or S-monomer, experiments with either R-monomer or S-monomer can be conducted.

[0067] Isotacticity is analyzed as is known in the art. 13C-NMR-spectroscopy can be used to determine the microstructure of the polymer obtained with a process of the present invention. For analysis it is possible to either evaluate the carbonyl signal at 169 ppm (see Fig. 2a) or the methylene signal at 40 ppm (see Figs. 2b-d). The ratio between the isotactic part of the polymer (mm and rm) and the syndiotactic part (rr and mr) has been evaluated.. Evaluated is the probability for meso-connections (Pm-value; meso = two adjacent centers having the same orientation). Fig. 2 shows some spectra of PHB examples in deuterated chloroform with different isotacticity ratios from 0.70 to 0.88.

[0068] The thermal properties of the polymer can be evaluated by DSC determination. It is the object of the present invention to provide polymers having a lower melt temperature than the isotactic PHBs known in the art. Fig. 3 shows the DSC diagram for a PHB example that has been obtained using the process of the present invention. It can be seen that the melting temperature Tm is 166°C and, thus, lower than the melting point of known polymers.

[0069] For molecular weight determinations, GPC analysis can be used as is known in the art, For polymers produced with the catalyst/initiator system of the present invention GPC analysis was carried out on a Polymer Laboratories GPC50 Plus chromatograph. As eluent, chloroform was used. Polystyrene standards were used for calibration.

[0070] It was found that the polymers obtained with a process of the present invention have very valuable properties. The mechanical properties are similar to those of petroleum based polymers like isotactic polypropylene and, therefore, can be used for similar applications, such as packaging. PHB polymers of the state of the art have a melting point which is close to the decomposition point, processability of these polymers is restricted. In contrast thereto the polymers obtained with the process of the present invention have a much better processability because their melting point is lower. Furthermore it has been found that when using the process of the present invention polymers are obtained which have a higher tensile strength than those isotactic PHBs known from the prior art. Thus, with the process of the present invention it is possible to improve the mechanical properties of PHB polymers. As those polymers have only some imperfections but otherwise are highly isotactic, they have a high biodegradability and can be used as biodegradable polymers. Furthermore, it has been found that other useful properties like barrier properties are maintained with the polymers of the present invention.

[0071] In summary the present invention provides a process for obtaining very valuable polymers with predeterminable parameters.


Claims

1. A process for polymerizing ß-butyrolactone comprising contacting racemic ß-butyrolactone or an enantiomer thereof with a catalyst/initiator system which comprises a rare earth metal, a chiral ligand, at least one nucleophilic ligand, at least one solvent ligand, and optionally an alkali based co-catalyst, wherein the chiral ligand is an enantiomer of a unit of formula I

wherein each Rz independently is linear or branched, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C5-C20 heteroaryl, or halogen;

wherein each Ra independently is H or an alkali metal.


 
2. The process of claim 1 wherein the catalyst/initiator system is a rare earth metal based complex which has been obtained by contacting a chiral ligand of formula I with a compound of formula II:

and optionally an alkali based co-catalyst,

wherein M is a rare earth metal,

each Rx independently is a nucleophilic ligand,

each Ry independently is a solvent ligand,

n is an integer from 1-5,

m is an integer from 0-5 with the proviso that n + m is an integer corresponding to the number of available association/bonding sites of the rare earth metal.


 
3. The process of claim 1, wherein the catalyst/initiator system is a rare earth metal based complex which has been obtained by contacting a chiral ligand of formula I with a rare earth metal compound of formula III, a solvent, and optionally an alkali based co-catalyst,
wherein the earth metal based compound is a compound of formula III

wherein M is a rare earth metal,

each X independently is halogenide, triflate, or C1-C20 alkoxide;

each Ry independently is a solvent ligand,

m is an integer from 0-5 and

contacting the complex obtained with an alkali salt of a nucleophilic ligand.


 
4. The process of one of the preceding claims wherein the catalyst/initator system is prepared in situ.
 
5. The process of one of claims 1-3 wherein the catalyst/initator system is isolated from the reaction mixture and added to a monomer composition comprising ß-butyrolactone.
 
6. The process of one of the preceding claims wherein the rare earth metal is yttrium, lutetium, scandium, ytterbium, terbium, samarium, lanthanum or a lanthanide, wherein optionally the rare earth metal is yttrium.
 
7. The process of one of the preceding claims wherein n is 1-3 and m is 1-3.
 
8. The process of one of the preceding claims wherein the monomer is racemic ß-butyrolactone.
 
9. The process of one of the preceding claims wherein the nucleophilic ligand is an amido group, an alkoxide or a di- or trialkyl methyl-silyl group, preferably a group selected from NRbRcRd, ORb and CHRbRc, wherein each of Rb,R,c and Rd independently is H or a group selected from linear or branched, substituted or unsubstituted C1-C20 alkyl, C6-C20 aryl, arylalkyl, silylalkyl.
 
10. The process of one of the preceding claims wherein at least one nucleophilic ligand is n N(SiHMe2)2 group.
 
11. The process of one of the preceding claims wherein at least one solvent ligand is tetrahydrofuran.
 
12. The process of one of the preceding claims wherein the co-catalyst is a lithium salt (LiN(SiHMe2)2) or wherein the co-catalyst is a potassium salt (K(N(SiMe3)2).
 
13. The process of one of the preceding claims wherein the catalyst has one of the following formulae:




 
14. Polyhydroxybutyrate polymer obtained with a process of one of claims 1-13.
 
15. Polyhydroxybutyrate polymer of claim 14 having a Pm between 0.6 and 0.9.
 




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Search report




Cited references

REFERENCES CITED IN THE DESCRIPTION



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Non-patent literature cited in the description