Patent Application
20190322803
The present invention concerns the preparation of poly(limonene)dicarbonate (PLDC) from sustainable starting materials, as well as the resulting PLDC products having an unusually high glass transition temperature.
The copolymerization of aliphatic epoxides and CO2 is a well-established approach towards the synthesis of thermoplastic polymers with properties that mainly depend on the nature of the epoxide monomer. Despite the fact that most reported polycarbonates are based on petroleum derived epoxide monomers such as cyclohexene oxide, propylene oxide and others, recently the attention has been shifting towards the use of (partially) bio-based epoxides as a way to produce polymers with an improved sustainability footprint. In this respect, the use of terpene oxides has yet offered new potential for biomass-derived polycarbonates and polyesters displaying similar or even improved properties compared to fossil fuel based conventional polymers.
Peña Carrodeguas et al. (Chem. Eur. J., 2015, 21, 6115-6122) disclose the copolymerization of limonene oxide (LO) and CO2 in the presence of PPNX (X═Cl, Br) co-catalysts and an amino-trisphenolate aluminum complex to produce poly(limonene)carbonate (PLC). Further articles to disclose the preparation of PLC include Byrne et al. (C. M. Byrne, S. D. Allen, E. B. Lobkovsky and G. W. Coates, Journal of the American Chemical Society, 2004, 126, 11404-11405), Li et al. (C. Li, R. J. Sablong and C. E. Koning, European Polymer Journal, 2015, 67, 449-458), Rieger et al. (Chem. Sci., 2017, 8, 1876-1882) and Hauenstein et al. (O. Hauenstein, M. Reiter, S. Agarwal, B. Rieger and A. Greiner, Green Chemistry, 2016, 18, 760-770), disclosing the use of zinc diiminate complexes as catalysts to promote the reaction.
Li et al. (Angew. Chem., Int. Ed., 2016, 55, 11572-11576) disclose the polymerization of limonene dioxide to prepare poly(limonene-8,9-oxide carbonate) (PLOC) and the further reaction of PLOC with CO2 to prepare PLDC. The PLDC prepared according to this method had a glass transition temperature of 146° C.
There is thus still a need for PLDC having higher glass transition temperatures, as well as improved methods for their preparation.
In one aspect, the present invention concerns a process for preparing poly(limonene)dicarbonate (PLDC) comprising the steps of:
In another aspect, the present invention concerns the PLDC resulting from the process of the invention. In a further aspect, the invention concerns PLDC having a glass transition temperature of at least 150° C.
A/Me
When referring to the amino-triphenolate catalyst
it will be referred to herein also as MMe. In the case of having a central aluminium atom, it is referred to as AlMe. In the case of having a central iron atom, it is referred to as FeMe.
When referring to bis-triphenylphosphine iminium halide, it will be referred to herein also as PPNhal, e.g. in the case of the chloride as PPNCI.
The meaning of the terms “limonene oxide” (LO), “poly(limonene)carbonate” (PLC), “poly(limonene-8,9-oxide)carbonate” (PLOC), and “poly(limonene)dicarbonate” (PLDC) are known to the person skilled in the art. The structures of these compounds, shown without stereochemistry, are:
Herein, the terms “halogen” and “halo” include fluoro, chloro, bromo, and iodo. Accordingly, “halide” includes fluoride, chloride, bromide, and iodide. In particular, chloride, bromide, and iodide are preferred.
Process
In one aspect, the present invention concerns a process for preparing poly(limonene)dicarbonate (PLDC) comprising the steps of:
a) reacting poly(limonene)carbonate (PLC) with an epoxidation agent to form poly(limonene-8,9-oxide)carbonate (PLOC),
b) reacting the PLOC obtained in step a) with CO2 to obtain PLDC. The PLOC obtained in step a) may be isolated and/or purified before being used in step b).
Several reactions for the epoxidation of carbon-carbon double bonds to the corresponding epoxide are known in the art. These include the Jacobsen-Katsuki epoxidation, the Prilezhaev epoxidation, the Sharpless epoxidation, and the Shi epoxidation. The epoxidation agents used in these and other reactions are well known and include peroxy acids, hydrogen peroxide, sodium hypochlorite, and potassium peroxymonosulfate (Oxone®). Thus, in one embodiment, the epoxidation agent is selected from a group consisting of peroxy acids, hydrogen peroxide, sodium hypochlorite, and potassium peroxymonosulfate. In another embodiment, the epoxidation agent is a peroxy acid. In a further embodiment, the epoxidation agent is meta-chloroperoxybenzoic acid.
For the addition of CO2 in step b) of the process according to the present invention, it has been found that it may advantageously be carried out in the presence of a halide catalyst. It has further been found that different halide catalysts provide satisfactory results. These include bis-triphenylphosphine iminium halide, such as bis-triphenylphosphine iminium chloride, ammonium halide, alkali metal halide, such as sodium bromide, and halides with β-diiminate complexes as disclosed by Li et al. (C. Li, R. J. Sablong and C. E. Koning, European Polymer Journal, 2015, 67, 449-458). In one embodiment, step b) is carried out in the presence of a halide catalyst. In another embodiment, step b) is carried out in the presence of bis-triphenylphosphine iminium halide as a catalyst. In a further embodiment, the bis-triphenylphosphine iminium halide is bis-triphenylphosphine iminium chloride. In still a further embodiment, step b) is further carried out in the presence of a Lewis acid, which may be in the form of a salt or a coordination complex of zinc, aluminium or iron. In a further embodiment, step b) is carried out in the presence of the amino-triphenolate co-catalyst having the formula:
wherein M is Al or Fe, R1, R2, R3, R4, R5, and R6 are independently selected from the group consisting of hydrogen, C1-C6 alkyl, such as methyl, C1-C6 haloalkyl, C1-C6 alkyloxy, halogen, cyano, and nitro, and L is selected from the group consisting H2O, tetrahydrofuran, and R—O—R′, R and R′ independently being C1-C6 alkyl. In one embodiment, the amino-triphenolate co-catalyst is MMe. In yet a further embodiment, M is Al.
The steps of the process according to the present invention may be carried out using various solvents capable of dissolving the reactants of the different steps. Such solvents are typically polar aprotic solvents. Such solvents are apparent to the person skilled in the art and include dichloromethane, chloroform, tetrachloroethane, acetone, toluene, methyl ethyl ketone, acetonitrile, dimethysulfoxide, dimethylformamide and dimethylacetamide. Step b) may advantageously be carried out using methyl ethyl ketone as a solvent. Hence, in one embodiment, step b) is carried out in methyl ethyl ketone as a solvent.
The PLC reagent used in step a) of the process according to the present invention may in principle be obtained according to any process known in the art. Such processes include those disclosed by Byrne et al., Li et al., Hauenstein et al., Rieger et al., or Peña Carrodeguas et al. In one embodiment, the PLC used in step a) is obtained by reacting limonene oxide with CO2 in the presence of a halide and the amino-triphenolate catalyst having the formula:
wherein M is Al or Fe, R1, R2, R3, R4, R5, and R6 are independently selected from the group consisting of hydrogen, C1-C6 alkyl, such as methyl, C1-C6 haloalkyl, C1-C6 alkyloxy, halogen, cyano, and nitro, and L is selected from the group consisting H2O, tetrahydrofuran, and R—O—R′, R and R′ independently being C1-C6 alkyl, as co-catalyst. In a further embodiment, the amino-triphenolate is MMe. In a further embodiment, the amino-triphenolate is FeMe or AlMe. In yet a further embodiment, the halide is chloride. In another embodiment, the halide is bis-triphenylphosphine iminium halide. In yet another embodiment, the bis-triphenylphosphine iminium halide is bis-triphenylphosphine iminium chloride.
As discussed above, the PLDC obtained according to the process of the present invention has a higher glass transition temperature than the PLDC disclosed in the prior art. Accordingly, the process of the present invention leads to a new PLDC product. Thus, one aspect of the present invention concerns a PLDC obtainable by the process according to the present invention. In a further aspect, the invention concerns a PLDC having a glass transition temperature of at least 150° C. In one embodiment, the PLDC has a glass transition temperature of at most 250° C. In another embodiment, the PLDC has a glass transition temperature of at least 160° C. In yet another embodiment, the PLDC has a glass transition temperature of at least 170° C. In still another embodiment, the PLDC has a glass transition temperature of at most 240° C. In a further embodiment, the PLDC has a glass transition temperature of at most 230° C. In still a further embodiment, the PLDC has a glass transition temperature of at most 220° C. In yet a further embodiment, the PLDC has a glass transition temperature of at most 210° C.
(+)-limonene oxide (4 mL, cis/trans mixture or cis), [AlMe] (74 mg, 0.14 mmol) and PPNCI (40 mg, 70 μmol) were mixed in a Teflon vessel equipped with a magnetic stirring bar, placed in a stainless steel reactor (reactor and vessel shown in
Table 1 summarizes the results obtained in the synthesis of PLC starting from different isomer mixtures of limonene oxide.
Thermal data (decomposition temperature) was obtained by differential scanning calorimetry/thermogravimetric analysis (DSC/TGA), polymer molecular weight (Mn) and dispersities (Mw/Mn) by gel permeation chromatography (GPC) measured against polystyrene (PS) standards with tetrahydrofuran (THF) as eluent at 25° C. Tg values (glass transition temperature) relate to the second heating run.
The NMR data for entry 5 are:
1H NMR (CDCl3, 400 MHz): δ (ppm)=5.09-5.03 (m, 1H), 4.73 (d, 2JHH=7.4 Hz, 2H), 2.41 (d, 3JHH=12.8 Hz, 1H), 2.25 (t, 3JHH=12.1 Hz, 1H), 1.93-1.73 (m, 3H), 1.71 (s, 3H), 1.65-1.57 (m, 1H), 1.52 (s, 3H), 1.43-1.31 (m, 1H). 13C NMR (CDCl3, 125 MHz): δ (ppm)=151.9, 148.6, 109.3, 81.8, 75.3, 37.4, 30.9, 30.6, 25.8, 21.5, 20.7.
PLC (1.74 g, 8.88 mmol of alkene units) as prepared according to Example 1 was dissolved in DCM (50 mL) and the flask placed in an ice bath. Subsequently meta-chloroperoxybenzoic acid (m-CPBA) (3.07 g, 17.7 mmol) was added portion-wise as a solid. Stirring was continued for 12 h, whilst the mixture was allowed to slowly warm to room temperature. The formed suspension was filtered and then saturated Na2SO3 solution was added under vigorous stirring to quench the excess of m-CPBA. Phases were separated and saturated NaHCO3 solution was added to the organic phase under vigorous stirring. After phase separation, the organic phase was washed with brine, dried over MgSO4 and all volatiles were removed in vacuo. If necessary, the polymer was additionally purified by precipitating the polymer with MeOH from DCM or washing the solid polymer with MeOH in an ultrasonic bath.
Thermal data was obtained by DSC/TGA, polymer molecular weight and dispersites by GPC measured against PS with THF as eluent at 25° C. Tg values relate to the second heating run.
The NMR data for entry 5 are:
1H NMR (CDCl3, 400 MHz): δ (ppm)=5.07-5.02 (m, 1H), 2.63-2.55 (m, 2H), 2.46-2.36 (m, 1H), 1.92-1.84 (m, 1H), 1.76-1.54 (m, 4H), 1.50 (s, 3H), 1.36-1.28 (m, 1H), 1.24 (s, 3H).
13C NMR (CDCl3, 125 MHz): δ (ppm)=151.8, 81.8, 74.8, 58.7, 53.1, 36.5, 30.0, 27.9, 22.6, 21.5, 18.1.
PLOC (200 mg, 940 μmol of epoxide units), PPNhal (94 μmol, 10 mol %) and solvent were mixed in a Teflon vessel equipped with a magnetic stirring bar, placed in a stainless steel reactor, purged three times with 5 bar of CO2, and pressurized with 20 bar of CO2 at room temperature. The mixture was heated to the desired temperature, as specified in Table 3, measured inside the reactor, and stirred for the time period specified in Table 3. After cooling down in an ice bath, the reactor was slowly depressurized. The liquid phase was transferred into a flask and the Teflon insert thoroughly rinsed with DCM. Removal of all volatiles in vacuum was followed by addition of DCM until the solid dissolved completely. Dropwise addition of MeOH gave a white to off-white precipitate. If necessary, the treatment was repeated to remove remaining PPNhal from the polymer. After drying in vacuum about 120-150 mg of the polymer could be isolated and used for further analysis.
Different combinations of AlMe catalyst and PPNhal co-catalyst were also tested in the HEL multireactor with glass test tubes as inserts under the following conditions: 20 bar initial CO2 pressure, 90° C., 24 h reaction time, MEK as solvent (0.24 M). These combinations gave the results indicated in Table 4:
PLOC (108 mg, 510 μmol of epoxide units), NaBr (6.3 mg, 61 μmol, 12 mol %) and N-methyl-2-pyrrolidone (NMP) (1.5 mL) were mixed in a Teflon inset of a stainless steel reactor, which was then pressurized with 25 bar of CO2. Subsequently, the reactor was heated to 98° C. inside temperature (corresponding to 130° C. at the stirring plate) and stirred at this temperature for 16 h. After that, the reactor was placed in an ice bath and depressurized. To the dark brown liquid methanol was added dropwise, leading to the precipitation of a brown solid. Repeated cycles of dissolution (in DCM) and precipitation (from MeOH) led to the isolation of an off-white solid, which was dried in vacuum.
The properties of the PLDC's prepared in this example are provided below in Table 5:
1541
1Measured with an edge temperature of 180° C. PLDCs of entries 1-5 of Table 5 were prepared following the procedure of Table 3, entry 2.
For entry 6, the conversion from PLOC to PLDC is carried out using the NaBr/NMP system as described above. Thermal data was obtained by DSC/TGA, polymer molecular weight and dispersities by GPC measured against PS standards with THF as eluent at 25° C. Tg values relate to the second heating run.
The glass transition temperatures for entries 5 and 6 show that the high glass transition temperature achieved with the process of the present invention does not depend on the catalyst for the conversion from PLOC to PLDC. On the other hand, without being bound by a particular theory, it seems that the way PLOC is prepared does have an influence since the PLOC prepared from PLC according to the present invention leads to higher glass transition temperatures than if the PLOC has been prepared from limonene dioxide according to Li et al. (146° C.).
The NMR data for entry 5 of Table 5 are:
1H NMR (CDCl3, 400 MHz): δ (ppm)=5.27-5.16 (m, 1H), 4.34-4.26 (m, 1H), 4.12-4.10 (m, 1H), 2.49-2.29 (m, 1H), 2.05-1.86 (m, 2H), 1.80-1.59 (m, 3H), 1.53 (s, 3H), 1.50-1.44 (m, 3H), 1.41-1.25 (m, 1H).
13C NMR (CDCl3, 125 MHz): δ (ppm)=154.4, 151.5, 84.9, 81.4, 74.2, 72.9, 38.2, 30.1, 26.1, 21.4, 22.8-20.5, 20.2.
This application claims the benefit of priority to U.S. Provisional Patent Application No. 62/659,556, filed on Apr. 18, 2018, the disclosure of which is hereby expressly incorporated by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 62659556 | Apr 2018 | US |
