Patent ID: 12240809

MEASUREMENT METHODS

In the following, reference is made to BHET for several solid compositions comprising at least 90 wt. % BHET (and hereinafter also referred to as BHET).

Purity

25 mg BHET is dissolved in 50 ml 100% acetonitrile, and measured with the HPLC “Agilent Technologies 1100 Series” with a “XBridge C8 3.5 μm, 4.6×150 mm” column. The detector is a DAD 242 nm.

The reported results (in table 1) are averages of Duplo measurements.

Bulk Density

The bulk density (below also referred to with p) is the weight of the material in a container of a certain volume. The value in the table is an average of a Duplo measurement. The protocol comprises:1. Tare a weighing scale with a 1000 ml measurement cylinder.2. Fill the cylinder with solid BHET and note the weight of the BHET.3. Determine the added volume of the BHET, by reading it from the measuring cylinder.

4.ρ[gcm3]=BHET[g]Filled⁢volume[cm3]

A 1000 ml measurement cylinder is used, so as to avoid wall-effects of the cylinder that would render the method less accurate. However, the determination of added volume sets a limit to the precision.

Skeletal Density

Skeletal density is determined with gas-pycnometry. The skeletal density takes into account that the density of the particles is reduced by the encapsulation of air bubbles. The protocol is:

The samples are degassed in vacuum at 25° C. for 16 h prior to measurement. The measurement was performed in accordance with ISO 12154: 2014 with the Quantachrome Ultrapycnometer 1000 at 25° C. A sample size of 150 cm3was used due to the large particle size distribution.

The reported values are averages of ten successive dependent measurements over a single representative sample with a maximum variation over these ten successive measurements of less than 0.08%. The estimated inaccuracy is determined using a standard deviation over a quality control material.

Porosity

The pore volume is determined with Hg-porosimeter. Prior to the mercury intrusion measurements, the samples were degassed in vacuum at 25° C. for 16 h. Subsequently, the intrusion and extrusion curves were recorded on a Micromeritics Autopore 9505 analyzer, applying pressures from 0.002 MPa up to 220 MPa. This pressure is converted to the pore diameter using the Washburn equation, wherein a value of 140° is used for the contact angle. The measurement was performed as in accordance with ASTM D 4404-10. Due to the limited size of the cell used in the mercury intrusion porosimetry and in order to have a fair comparison among the samples, only particles with a size smaller dan 0.6 mm were used for the test.

The porosity (%) is calculated on the basis of these measurements.

Apparent Density

The apparent density is the density calculated on the basis of the mercury intrusion porosimetry.

Angle of Repose

The angle of repose is defined as the angle from a horizontal plate to the free surface of a powder under gravitational force. The so-called tilting method is used for the measurements. It is known that this tilting method generally results in higher values than other methods such as the injection method. Use was made of a drum with a diameter of 153 mm and a height of 45 mm. Approximately 200 ml of sample was placed inside the drum. The rotation speed of the drum was set to 6.4 rpm. Three photographs are made during rotation of the drum and the angle of repose is determined optically from each of the photographs. The provided value is the average.

Rate of Dissolution in Ethylene Glycol

The dissolution of BHET is measured at two temperatures: T1=140° C. and T2=180° C. The measurement method protocol is:

First, heat 95 g of ethylene glycol (EG) to T1or T2in a 250 ml beaker glass closed off with a watch glass or aluminium foil. A heating plate of the type IKA C-MAG HS7 was used with the stirrer speed set at 1.5, on a scale up to 6. With a thermocouple, it was ensured that the solution did not overheat. When the EG has reached the specified temperature (T1or T2), remove the watch glass or the aluminium foil and add 5 g solid BHET in one uninterrupted movement. The settings for temperature and stirring speed remain unchanged. The temperature drops due to the implementation of BHET at room temperature, which the thermocouple will respond to.

Then, the dissolution time is registered: With a video camera, the introduction of BHET and its dissolving in EG is recorded. These recordings are studied in slow motion to visually determine when all solids are dissolved.

The value in the table is an average of a Duplo measurement.

For the BHET in accordance with the invention, the measurement has been carried out on the basis of BHET as obtained after fluid bed drying and on the basis of samples on which a size reduction treatment was carried out to arrive at a size of 5 mm as defined by sieving.

Rate of Melting in Molten BHET

The melting of BHET is measured at two temperatures: T1=140° C. and T2=180° C. The measurement method comprises the steps of:

First, the BHET melt is prepared. Thereto 47.5 g of BHET is heated to T1or T2in a 250 ml Erlenmeyer which is submerged in a paraffin oil bath. This results in formation of the melt. The Erlenmeyer with BHET is kept at least 15 min. in the oil bath to ensure a homogenous temperature of the melt. Both the melt and the oil are stirred with a stirring speed of 1.5 (on a scale up to 6) on a heating plate of the type IKA C-MAG HS7. A thermocouple is used to keep the oil bath at constant temperature.

As a second step, solid BHET is added to the BHET melt. 2.5 g solid BHET is added in one uninterrupted movement. The settings for temperature and stirring speed remain unchanged. Then, the melting time is measured, using a video camera: The introduction of BHET and its melting is recorded. These recordings are studied in slow motion to visually determine when all solids are dissolved.

For the BHET in accordance with the invention, the measurement has been carried out on the basis of BHET as obtained after fluid bed drying and on the basis of samples on which a size reduction treatment was carried out to arrive at a size of 5 mm as defined by sieving.

The value in the table is an average of a Duplo measurement.

EXAMPLES

Example 1: Preparation of the BHET According to the Invention

A mixture of flakes of polyethylene terephthalate (PET), ethylene glycol (EG) and a catalyst was used in a mutual ratio in the range. In an example on laboratory scale in a 100 mL flask, 1 g of dry catalyst complex was used in combination with 5 g of PET and 50 g of EG. The catalyst complex was prepared by starting from magnetite nanoparticles (size 5 nm), trisilanolpropyl (C3H7Si(OR)3, wherein R (ethyl) and (bim)FeCl4or (bim)Cl. Herein bim refers to butylimidazolium. The catalyst complex was prepared by a reaction of the (bim) FeCl4or (bim) Cl with the trisilanolpropyl. The resulting functionalized propyltrisilanol was brought into contact with the nanoparticles so as to form an aggregate in the manner specified in WO2017111602, which is included herein by reference. However, the use of alternative catalysts is not excluded. The catalyst complex dispersion was homogenised by shaking for 5 minutes by hand. To 10 g of catalyst complex dispersion 41 g of EG was added and the liquids were shortly mixed by hand to homogenise the dispersion. Then, 5 g of PET flakes were added and the round bottom flask was placed in the heating set up. The PET flakes were prepared from coloured PET bottles such as commercially available blue coloured bottles and red coloured bottles. The heating was started and within 20 minutes, the reaction mixture had reached the reaction temperature of 170-200° C.

The depolymerisation was repeated in a 1000 liter vessel. The degradation reaction was carried out at a temperature in the range of 180-210° C. The concentration of the catalyst complex was about 0.5 wt. %, which was not very critical. After a predefined duration of the reaction, for instance 60-180 minutes, the reaction mixture was cooled down. Water was added and the mixture was led to a centrifuge for separation. This treatment resulted in a first hydrophilic solution and a second phase. The hydrophilic solution contained a mixture of water and the solvent, ethylene glycol. The second phase was in the form of a slurry, which contained a significant portion of solid material. At least 95% of the flow entering the centrifuge became hydrophilic solution. Typically, this was over 98%, or even over 99%. The hydrophilic solution was led via a membrane filter to remove solid material to an adsorbant, i.e. active coal.

The hydrophilic solution was transferred to a dimer crystallisation stage, which was in the example a mixing vessel that is provided with temperature regulation means for bringing and keeping the crystallizing solution at a predefined temperature, for instance in the range of 50-70° C., such as 57-64° C., for instance 60° C. The exact temperature will depend on the concentration of the dimer, the ratio between water and ethylene glycol and the desired residence time. After a sufficient degree of crystallisation, the resulting combination of first mother liquid and dimer crystals was transferred to a separator, for instance a filtration unit.

Downstream thereof, the BHET is crystallized and recovered in a further separator. Crystals were obtained in a purity of more than 90 wt. %, based on dry weight. In the example used, the crystallisation of BHET occurred at a lower temperature relative to the dimer crystallisation. The BHET crystals were thereafter washed with water, so as to remove any adsorbed mother liquid. The material has a humidity content of 28-40 wt. % and is in the form of a cake.

A test was carried out on labscale to identify purity. BHET crystalline material was obtained starting from a hydrophilic solution of 520 gram containing 35.4 gram BHET (6.8 wt. %), 3.6 gram dimer (10.8 wt. % relative to BHET) and 50 ppm Fe. The wet BHET was washed and thereafter dried in a laboratory scale drying equipment. The overall dimer content in the dried BHET was 1.5 wt. %, and the Fe content 20 ppm.

Example 2

500 gram of said crystallized and washed material was thereafter subjected to size reduction and drying. Size reduction occurred by means of pressing through a sieve with a sieve of 5 mm (opening). The resulting material—granules—was thereafter dried in a fluid bed dryer, with air as the carrier gas. The temperature of the carrier gas was 90° C. The flow rate was initially in the range of 0.9-1.2 kg/(m2·s) and typically reduced to 0.8 kg/(m2·s) after 10 minutes. Use was made of a batch type of a so-called shaking fluid bed dryer suitable for 1 liter of product per batch. The drying time was between 14 and 20 minutes. The resulting humidity content reduced from 1.5 wt. % to 0.1 wt. % as a function of the drying time. The material was white. No contamination was visible.

Example 3

Crystalline BHET material as obtained in Example 1 with a humidity content of 36 wt. % and in the form of a cake was processed by means of a nibbler for size reduction to obtain granules. Thereafter, the resulting, granulated material was subjected to fluid bed drying. A white material was obtained without any visible contamination. This material was further evaluated.

Comparative Example 1

The crystallized BHET obtained in example 1 after the washing step was dried by means of vacuum drying.

Comparative Example 2

BHET was obtained from Sigma-Aldrich (product number 465151) and was delivered in a poly bottle. The purity was at least 94.5 wt. %. (GC) according to specifications of the supplier.

Evaluation of Shape and Purity

An evaluation was made of the shape, particle size distribution and the purity of the material. The results are shown in Table 1. The material of the invention was a granulate, wherein individual particles had varying size and were characterized by irregular shapes and a non-smooth surface. In one test, a small size distribution was chosen from the material. It was found that the purity of this size fraction did not deviate from the overall purity. The purity is herein measured on the basis of HPLC. The material of comparative example 1 was stone-like, with rather smooth surfaces. Purity measurements demonstrated a larger variation. The material of comparative example 2 was in the form of flakes. The purity turned out higher than the minimum purity indicated by the supplier.

TABLE 1measured parametersParticledimensionsPurityShapeand size(wt. %),ExampleShapecharacterisationdistributionHPLC3-1GranulateNon-smoothWide size97.63-2Granulatesurface,distribution95.5irregular shapes(spheres,elongatedspheres)3-3GranulateNon-smoothSmall size96.6surface,distribution:irregular shapes4-6 mm(spheres,diameterelongatedspheres)Comp 1-1Stone-likeSmooth surface,Wide size93.3Comp 1-2Stone-likespheresdistribution:98.9Fines - cmscaleComp 2-1FlakesSmooth surface,Wide size98.7Comp 2-2Flakesflat flakesdistribution:98.7cm scale

The wide size distribution of the examples according to the invention were further specified as that 99% was smaller than 6.3 mm and 70% was smaller than 2.4 mm, as based on particle sieving. In further experiments using laser diffraction, using 0 bar venturi pressure, the volume particle size distribution as specified in Table 2 was measured. The data are herein averages of two separate measurements:

TABLE 2meaningValueDoMinimum particle size0.14mmD1010% of particle volume smaller than the0.65mmtabled valueD50Median particle size1.30mmD9090% of particle volume smaller than the2.40mmtabled valueD100100% of particle volume is smaller than3.50mmthe tabled valueD [4, 3]Volume weighted mean diameter1.42mmSpanDistributed width, calculated as (D90−1.4(—)D10)/D50Mode 1Modal size, particle diameter present1.4mmwith highest frequency

It is observed that the values obtained with the laser diffraction measurements do not include particles with a size beyond 3.5 mm, which are present. It is estimated that the results are applicable for the 70% that was sieved through the 2.36 mm sieve. Hence, it can be concluded that the granulate in accordance with the invention, at least in one preferred embodiment, has a mean diameter, as measured by laser diffraction (excluding particles beyond 3.5 mm), in the range of 1.2-1.6 mm, said mean diameter being defined as the volume weighted mean diameter ((ΣniDi4)/(ΣniDi3). Preferably, said mean diameter is in the range of 1.3-1.5 mm. The mean diameter is in the range of 1.1-1.5 mm, preferably 1.2-1.4 mm. The distribution width is in the range of 1.3-1.5.

Test of Densities and Porosity

Measurements of density and porosity were hereinafter carried out as described above. Results are shown in Table 3. For the material of the invention, a separate test was carried out with relatively large granules. The larger granules fraction corresponds to the fraction 1-3 indicated in Table 1. The general fraction additionally includes smaller granules. In other words, the larger granules fraction is a portion of the general fraction. The sample including larger granules corresponds better to the particle size present for the comparative samples.

TABLE 3densities (values are averaged), pore volume and porosity. Sample1A indicates a fraction of sample 1 based on large granules.BulkSkeletalApparentPoreDensitydensitydensityvolumePorosityExample(g/cm3)[g/cm3][g/cm3][cm3/g](%)30.531.3371.340.5844%3A——1.350.4337%Comp 10.641.3011.330.045%Comp 20.591.3711.400.045%

The skeletal densities are in the range of 1.301-1.371 g/cm3. The maximum absolute error for the measurement is approximately 0.005 g/cm3. Therefore, although the differences are small, the skeletal densities of all samples are significantly different. These differences in density can be caused by impurities and/or by inaccessible voids in the materials.

The bulk densities are significantly lower than the skeletal densities. This is the result of the presence of pores, both intra-particle pores and inter-particle pores. A further contribution to the bulk density is obtained from hollow spaces between the samples when filling the beaker. Given that the particles of the comparative examples are larger, the contribution of the hollow spaces is more significant for the comparative examples. Still, it is apparent from Table 1 that the bulk density for the sample of the invention is lower than that of the comparative examples. This is due to the increased porosity.

It is immediately visible that the pore volume of the sample of the invention is significantly larger than that of the comparative samples. The pore volume of the larger granules fraction is lower. It is understood by the inventors that selective variation of the pore volume can be obtained by means of the settings of the processing steps after crystallisation (size reduction and fluid bed drying). Mercury intrusion and extrusion curves for the sample of the invention are shown inFIG.1Herein, the intruded volume (cm3/g) is shown as a function of the applied pressure (MPa). The extrusion curves are shown with open dots (starting at 0.1 MPa), the intrusion curves with massive dots. The upper curves relate to the normal samples, the lower curves relate to the samples obtained from larger granules. The curves show initial intrusion from a low pressure of approximately 0.002 MPa up to approximately 0.05 MPa. This initial intrusion should be attributed to the rearrangement of particles and the filling of inter-particle voids. It can be easily seen that this step is much lower for the larger granules fraction. The intrusion curves show a very similar second intrusion step ranging from approximately 0.1-10 MPa. Such contribution presumably is to be attributed to intra-particle void contribution. From a pressure of 10 MPa upwards a nice plateau is reached. This observation is an indication that all porosity of pores of at least 6 nm is adequately assessed. The pore size of 6 nm is the lower limit of the mercury intrusion porosimetry technique.

Quantitative information on the total pore volume and the porosity derived thereof is summarized in Table 3. Since compression occurs, use is made of results at different pressures so as to exclude the compression in the calculations.

The obtained apparent densities can be correlated to the skeletal densities. Only very minor differences are obtained, with a maximum relative deviation of 5%.

Pore size distributions have been derived from the intrusion curves. The result is shown inFIG.2. Two major contributions are therein visible. First of all, there is an inter-particle contribution from 50-700 μm, with a mode around 415 μm. This can be attributed to the filling of inter-particle pores. A second contribution ranges from approximately 0.3-10 μm with a mode at 4 μm. This contribution should be attributed to the filling of intra-particle pores.

Intrusion curves for the comparative examples are at significantly lower levels reaching up to a maximum of approximately 0.04 cm3/g, rather than 0.4 cm3/g for the larger granule fraction. In the derived pore size distributions, the intra-particle contribution in the range of 0.03-10 μm is almost entirely absent.

Evaluation of Flow, Melting and Dissolution Behaviour

The behaviour of the material upon melting in molten BHET and dissolution in ethylene glycol was tested. This behaviour is important for the intended re-polymerisation of the material. Results are shown in Table 4. Furthermore, the angle of repose is indicated. This parameter is indicative of the flow behaviour. Results are shown in Table 4. The test was carried out in duplo. The sample of the invention was furthermore measured twice: for the second experiment a size reduction was carried out. Moreover, the test is carried out at two different temperatures.

TABLE 4dissolution and melting timesDissolution times/melting times in seconds inethyleneethylenemoltenmoltenglycol atglycol atBHET atBHET atExample140° C.180° C.140° C.180° C.Remarks3-11645725Without size reduction3-2875419Without size reduction3-374237After size reduction to 5 mm3-463198After size reduction to 5 mmComp 1-157239335Comp 1-246298941Comp 2-116123815Comp 2-22094716

The results in Table 4 indicate that melting and dissolution is worst for comparative example 1. This material includes the same crystallized BHET as that of the invention, but is thereafter processed in a different manner arriving at low porosity rather than high porosity. The melting and dissolution times for the material of the invention without size reduction and that of comparative example 2 are comparable. However, it should be understood that this is not deemed an appropriate comparison, as the volume per particle of the samples 3-1 and 3-2 of the invention is larger than that of the comparative examples. When performing a further size reduction to arrive at comparable volumes, the dissolution and melting times of the material of the invention are clearly shorter.

TABLE 5angle of repose. All values in degrees. The standarddeviation indicates the 95% confidence interval.MeasurementStandardExample123Averagedeviation335.436.937.336.52.5Comp 145.048.042.245.17.2Comp 248.350.648.649.23.1

Table 5 indicates the angles of repose. Therein, the 95% confidence interval is calculated according to the students-t-method with 3 observations. Based on the confidence interval, the Comparative Example 2 is significantly different from that of the invention. The Comparative Example 1 is quite different. However, due to the higher standard deviation, no statement can be made as to the statistically significant difference. The material of the invention has the lowest angle and is thus best flowable.

These results correspond with the observations as to shape. The material of comparative example 2 is in the form of flakes. This shape can be expected to have worst flowability. Another important factor is the particle size distribution. A narrow particle size distribution will promote a better flowability. The material of Comparative example 1 has the broadest particle sized distribution of all samples. Hence, it is not surprising that its flow behaviour is not good.

This application is based on Netherland Patent Application Serial No. 2023686 filed with Netherland Patent Office on Aug. 22, 2019, the entire contents of which are hereby incorporated herein by reference.