Title of Invention

"A METHOD FOR PRODUCING POLYTRIMETHYLENE TEREPHTHALATE"

Abstract A method for producing polytrimethylene terephthalate which comp rises polycondensation of 1,3-propane diol and dimethylterephthalate or terephthalic acid followed by solid state polymerization of the polycondensation reaction product to increase the intrinsic viscosity, which comprises quenching the solid state polymerization product in water at a temperature of from 0 to 18°C followed by pelletization of the quenched product. Figure 1
Full Text REDUCTION OF FRIABILITY OF POLY(TRIMETHYLENE TEREPHTHALATE)
Field of the Invention
Unlike poly(ethylene terephthalate) (PET), poly(trimethylene terephthalate) (PTT) becomes friable after being crystallized and, especially, after being further polymerized in the solid state (SSP). Because of its friability, during conveying and shipping of crystallized or solid stated PTT, which is usually in pellet form, excessive amounts of dust and fines are generated, incurring a substantial material loss and creating problems during subsequent processing. Three unexpected ways to increase the robustness of crystallized and solid stated PTT pellets have been discovered, thereby minimizing dust and fines generation problems during handling of such PTT pellets. Background of the Invention
PTT is a newly commercialized polyester whose properties and processes for manufacture are similar to those of the well-known and most widely used polyester, PET. PTT possesses a unique combination of properties suitable for fibre and engineering plastic applications. For fibre applications, the required intrinsic viscosity (IV) of PTT is between 0.80 and 0.94 dl/g (equivalent to number average molecular weights of 18,000 and 20,000 respectively). This is approximately the same number average molecular weight range for PET used in textile fibre applications. PTT for fibre applications can be advantageously produced by a combination of a melt
polymerization process and a solid state polymerization (SSP) process because of the reasons given below.
Because PTT is substantially less stable than PET and hence more susceptible to thermal degradation than PET in melt state, the melt polycondensation of PTT should be conducted at temperatures at least 30°C below that for PET. Furthermore, because the major polycondensation by-product of PTT, 1,3-propanediol (PDO), is substantially less volatile than that of PET, ethylene glycol (EG), a thin-film type polycondensation reactor, such as a disk-ring reactor, should be used -to effectively remove the polycondensation by-products to achieve the IV required for fibre-grade PTT. Consequently, a polycondensation time several times longer than for PET and a disk-ring type polycondensation reactor several times larger than for PET should be used for PTT. It is a very expensive process if a melt polymerization process alone is used to produce PTT for fibre applications. Furthermore, even at such lower melt polycondensation temperatures, the long residence time required to achieve the desired IV will result in inferior product properties, especially colour. By terminating melt polycondensation earlier, to limit thermal degradation, and further polymerizing the melt polycondensation product in solid state at a much lower temperature to the IV suitable for the desired application, better overall process economics and superior product quality, especially in-terms-of colour, can be achieved.
When the desired IV is reached, the melt polycondensation product is usually extruded through a strand die to produce melt strands, which are quenched with water (quenching water) to solidify them, which are
then chopped into pellets with a pelletizer. The PTT pellets thus obtained may be used directly for fibre spinning, if the IV is sufficiently high, or otherwise used as a prepolymer for further polymerization in solid state.
In the pelletizing system for polyesters, including PET and PTT/ deionized water (DI water) or soft water is used as the quenching water to protect the equipment, especially the cutter. The spent DI water, which is warm, is recycled after being cooled in a heat exchanger usually with utility water, which, in turn, is usually cooled in a cooling tower. Therefore, the temperature of the "quenching water is usually somewhat higher than room temperature (i.e. 77°F or 25°C). It is not unusual that the quenching water temperature gets as high as 104°F (40°C) during the summer time.
Because of the relatively low Tg (about 45°C) and relatively high crystallization rate, PTT pellets thus obtained have a crystallinity of between 10 and 20 wt. % (vs. 3-5 wt.% for PET pellets). Nevertheless, for convenience, the PTT pellets thus obtained are referred to as "amorphous" pellets.
Crystallization of the pelletized amorphous PTT is required for the following reasons:
1. To prevent blocking of amorphous pellets during
shipping or storage in summer months.
2. To prevent sticking or agglomeration of pellets
during drying prior to spinning.
3. To prevent sticking of pellets during solid state
polymerization.
In the summer months, the interior temperature of a rail car or an exposed storage silo can reach as, high as 140°F (60°C), exceeding the Tg of PTT. Under these
shipping and storage conditions, amorphous PTT pellets become tacky and stick together to form blocks. To prevent blocking of PTT pellets during shipping or storage in the summer months, PTT pellets must be crystallized to achieve a crystallinity of at least 36%. Crystallization of PTT can be most efficiently conducted at temperatures between 140 and 170CC. Because sticking of pellets occurs before the pellets develop a sufficient crystallinity, crystallization is usually conducted under vigorous agitation in a mechanically agitated vessel, a tumble vessel, or a fluidized bed. The typical crystallization time is between 10 minutes and one hour, depending on the type of crystallizer used.
To minimize hydrolytic degradation of PTT during melt processing, such as spinning, PTT must be dried to a moisture content below 0.005% beforehand, usually also at temperatures between 140 and 170°C. To prevent sticking during drying, amorphous PTT pellets must be precrystallized, usually at the same temperature used for drying. Once PTT pellets are sufficiently crystallized, they can be dried in a moving bed or a drying hopper without sticking. Therefore crystallization and drying of PTT can be conducted in the same vessel or in two different vessels. Although, in large-scale operations, crystallization and drying of PTT are most economically conducted in separate vessels, "at many fibre-spinning facilities, tumble dryers are used to crystallize and dry polyesters.
SSP of PTT is effected at 190°C or higher temperatures. To prevent PTT pellets from sticking together or to the reactor wall, amorphous PTT prepolymer must be crystallized at an early stage of the SSP process.
It has been found that PTT pellets produced by conventional process, unlike PET pellets, become brittle or friable after undergoing crystallization or SSP. Because of the friability of the pellets, excessive amounts of dust and fines can be generated during shipping and conveying of crystallized or solid stated PTT products, incurring a substantial material loss and -creating problems in the downstream operations. The most pronounced dust and fines generation occurs in high-speed pneumatic conveying systems, such as. a dilute phase conveying system. Material losses as high as 15% through dust and fines generation during conveying of solid stated PTT have been reported. Summary of the Invention
It has been unexpectedly discovered that the friability of crystallized PTT and solid stated PTT can be effectively reduced by lowering the temperature of the quenching water used in the pelletizing of the melt polycondensation polymer to between 32°F (0°C) and 65°F (18°C). In addition, it has also been discovered that the robustness of solid stated PTT pellets is effectively increased by using a prepolymer with a lower IV or by increasing the IV of the solid stated product. The normal range for prepolymer IV is 0.60 to 0.70 dl/g. In the present invention, it should be 0.35 to 0.70 dl/g. The normal range for SSP IV is 0.80 to 0.94 dl/g. For the present invention, it should be 0.80 to 2.00 dl/g.
Thus, in accordance with the present invention there is provided a method for producing polytrimethylene terephthalate which comprises polycondensation of 1,3-propane diol and dimethylterephthalate or terephthalic acid followed by solid state polymerization of the polycondensation reaction product to increase the
intrinsic viscosity, which comprises quenching the solid state polymerization product in water at a temperature of from 0 to 18°C followed by pelletization of the quenched product. Preferably, the polycondensation is carried out such that the polycondensation reaction product has an intrinsic viscosity of from 0.35 to 0.70 dl/g. Preferably, the solid state polymerization is carried out such that the solid state polymerisation product has an intrinsic viscosity of from 0.80 to 2 dl/g.
In accordance with the present invention there is also provided a method for producing polytrimethylene terephthalate which comprises polycondensation of 1,3-propane diol and dimethylterephthalate or terephthalic acid followed by solid state polymerization of the polycondensation reaction product to increase the intrinsic viscosity, which comprises carrying out the polycondensation such that the polycondensation product has an intrinsic viscosity of from 0.35 to 0.70 dl/g. Preferably, the solid state polymerization product is quenched in water at a temperature of from 0 to 18°C. Preferably, the solid state polymerization is carried out such that the solid state polymerization product has an intrinsic viscosity of from 0.80 to 2 dl/g.
In accordance with the present invention there is further provided a method for producing polytrimethylene terephthalate which comprises polycondensation of 1,3-propane diol and dimethylterephthalate or terephthalic acid followed by solid state polymerization of the polycondensation reaction product to increase the intrinsic viscosity, which comprises carrying out the solid state polymerization such that the solid state polymerization product has an intrinsic viscosity of from 0.80 to 2 dl/g. Preferably, the polycondensation is
carried out such that the pblycondensation reaction product has an intrinsic viscosity of from 0.35 to 0.70 dl/g. Preferably, the solid state polymerization product is quenched in water at a temperature of from 0 to 18°C. Brief Description of the Drawings
The present invention will now be described by way of example with reference to the accompanying drawings, in which:
Figure 1 shows the effects of prepolymer pelletizing quenching water temperature on friability test failure rates of solid stated products of 0.653 IV PTT prepolymer;
Figure 2 is a plot of the crystallinity versus SS? time for a prepolymer solid stated at different temperatures;
Figure 3 shows the effect of SS? temperature on the friability test failure rate of SSP product of 0.653 cl/g IV PTT prepolymer;
Figure 4 shows the effects of prepolymer pelletizing quenching water temperature on the friability test failure rates of SSP products of 0.545 dl/g IV ?TT prepolymer; and
Figure 5 shows the effect of SE? temperature on the friability test failure rate of SSP product of 0.545 dl/g IV PTT prepolymer. Detailed Description of the Invention
Quenching the SSP product in water rather than cooled air has distinct advantages. Polymer cooled in water is less friable than polymer cooled in cold air. Water can remove fines stuck on the pellet surfaces better than air and a cleaner produce is the result. Water cooling systems are more compact and cheaper than
air cooling systems. Pollution control is much easier with a water cooling system. Density and Crystallinity
The density of PTT pellets was measured in a density gradient column.
The crystallinity of PTT pellets can be determined either by the DSC method or by the density method. It should be noted that the crystallinity values determined by the two methods might be quite different because each method employs different sets of assumptions. Because the density method is quicker and simpler and yields more consistent results, it was used exclusively to determine crystallinity. All the PTT resins used in the experiments were delustered PTT resins containing 0.4% by weight of titanium dioxide (TiO2) delustrant. The polymer density
was calculated from the sample (pellet) density using the density value of 3.90 g/cm3 for TiO2 • The weight percent crystallinity of the polymer, Xc, is related to the polymer density by following equation:
(Equation Removed)
where D is polymer density, Dc (=1.42 g/cm3) and Da
(=1.29 g/cm3) are densities of 100% crystalline PTT and truly amorphous PTT (with 0% crystallinity) respectively. Friability Test
A simple test method has been developed to determine the relative friability or robustness of PTT pellets. The apparatus consists of two flat metal plates. The test pellet is laid on its side between the two plates. Then a fixed force is applied to the top plate in an attempt to crush the pellet. With crystallised or solid
stated pellets, four possible outcomes are observed. The pellet may remain intact, crack, break into a few pieces, or shatter into many small pieces. Kith amorphous pellets, another outcome in addition to these four is possible, i.e. the pellet may be flattened with or without cracks at the edge, but not troken. A fixed force of 105 1bf (467 Newtons) was used for all the
friability tests and 20 pellets were tested for each sample. For the sake of simplicity, pellets that remained' intact, were flattened, or were cracked in the test were considered to pass the test;, and those that were broken or shattered were considered to fail the test. Thus a failure rate in terms cf percent of pellets that fail was obtained for each sample. This is reasonable because as long as the pellets are not broken off or rubbed off in the conveying lines or the shipping vessels, no material loss is incurred or no harm is done. The failure rate is a useful measure for the friability or robustness of polyester pellets. The higher the failure rate, the more friable or the less robust are the pellets. It should be noted that, tc have a fair comparison, all test pellets should have similar size and shape, because a bigger pellet, for example, will have a greater mass to dissipate the fixed force applied and is less likely to fail than a smaller pellet, all else being equal. Pelletization
PTT resins produced in a production-scale melt polycondensation plant were extruded and pelletised with a small extruder and a small pelletizer for the experiments. There were two reasons for the pelletization: (1) to prepare pellets with similar size and shape, and (2) to test effects of quenching water
temperature on the friability of crystallized and solid stated PTT. The shapes of polymer pellets produced by two different pelletizing systems may be quite different and may yield quite different friability test results even if they have similar friability. Furthermore, it is very difficult, if not impossible, to change the temperature of the quenching water in the palletizing system of a polyester resin production plant. Therefore, to determine the effect of pelletizing quenching water temperature on the friability of crystallized or solid stated PTT pellets, it is necessary to use an experimental pelletizing system to produce the PTT pellets of similar size and shape for testing.
The pelletizing system used to prepare PTT pellets
for the experiments consisted of a 1 1/4 in. (3.2 cm)
extruder (Model KL-125 manufactured by Killion Extruders, Inc., Cedar Grove, NJ) fitted with an strand die having a 3/16 in (0.48 cm) diameter hole, a 8 in. W X 6 in. D X 8 ft L (20.3 cm W X 15.2 cm D X 243.8 cm L) quenching water trough, and a laboratory pelletizer (Model PELL 4 manufactured by Berlyn Corp., Worcester, MA) . The resin to be pelletized was dried in a vacuum oven at 140CC overnight prior to pelletizing. During pelletizing, the extruder barrel temperature and the die temperature were set at 265°C and the water trough was filled with quenching water with the desired temperature, which ranged from 32°P (0"C) to 105°F (40.6"C). The quenching water with each desired temperature was prepared by mixing tap water with ice or hot water. For example, quenching water with 32°F of temperature was prepared by mixing ample amounts of crushed ice with cold tap water. The pre-dried PTT resin was extruded through the single-
hole die to form a melt strand, which was quenched in the water trough to solidify, and then was chopped into pellets in the pelletizer. The pellet size was controlled by adjusting the screw RPM of the extruder and/or the cutter RPM of the pelletizer. The pellet size was controlled to within the range of 2.42 - 2.56 g/100. The resulting pellets had a cylindrical shape, with a typical length of 3.3 mm, a typical major diameter of 3.1 mm, and a typical minor diameter of 2.2 mm. Within this range, the effect of the pellet size on the friability test result is negligible. For each pelletization run, the amount of polymer pelletized was limited to no more than 1.5 pounds (0.68 kg) so that the quenching water temperature rose by no more than 2°F (1°C) during the run. Solid state polymerization experiments
All SSP experiments were conducted in a small-scale reactor made of a 24-inch (61 cm) long glass tube with about 1.25-inch (3.2 cm) inner diameter. This tube-shaped SSP reactor had a cone-shaped bottom, which was connected to a small purge-gas supply tube, which in turn coiled up around the reactor. The only purge gas used was nitrogen. The reactor with its purge-gas supply tube was immersed in a thermostated oil bath that heated the incoming nitrogen as well as the reactor content.
Initially, the oil temperature was controlled at 170°C. About 100 grams of PTT pellets was charged into the reactor and a stream of nitrogen, sufficient to fluidize the PTT pellets in the reactor, was passed through the reactor to effect crystallization of the PTT pellets. After the crystallization step, which lasted 15 minutes, the nitrogen flow was reduced to 18 standard cubic feet per hour (SCFH) (509.7 litres per hour) to
maintain a static bed and the oil temperature was maintained at 170°C for another hour to dry the PTT pellets. Then the oil temperature was raised quickly to the desired SSP temperature, which ranged from 190 to 225°C, and the nitrogen flow was again increased to fluidise the PTT pellets for 15 minutes, during which the PTT pellets were preheatsd to the SSP temperature' After the preheating step, the nitrogen flow was again reduced to 18 SCFH (509.7 litres per hour) to maintain a static bed to start the SSP step. Except for the 190°C SSP runs, the SSP step of each run lasted 22 hours. For the 190°C SSP runs the SSP step lasted longer. Samples were taken at various intervals throughout the SSP step. Example 1
An amorphous PET sample with an IV of 0.593 dl/g and a pellet size of 2.46 g/100 and a solid stated PET sample with an IV of 0.842 dl/g and a pellet size of 0.250 g/100 were subjected to the friability test. All the amorphous PET pellets tested were slightly flattened and all the solid stated PET pellets tested remained intact, indicating that neither the amorphous PET pellets nor the solid stated PET pellets were friable. Example 2
A sample of amorphous delustered PTT (containing 0.4 wt.% TiO2) with an IV of 0.635 dl/g and a pellet size of 2.45 g/100 (referred to as Polymer A) produced in a batch melt polymerization plant was subjected to the friability test. The average quenching water temperature used in pelletizing this PTT resin was 78°F (25.6°C). All pellets tested were somewhat flattened, but not cracked or broken. This indicates that, with a sufficiently high IV, amorphous PTT pellets are ductile and not friable.
Example 3
A sample of solid stated delustered PIT with an IV of 0.887 dl/g (referred to as Polymer B) produced in a commercial solid state polymerization plant, with the amorphous PIT in Example 2 as the prepolymer, was subjected to the friability test. The PTT pellets had been solid stated in a continuous SSP reactor at temperatures between 192 and 198°C for about 10 hours. All pellets tested were shattered, indicating this solid stated PTT sample was very friable. Example 4
Polymer A in Example 2 was pelletized using quenching water temperatures of 78°F (25.6°C), 52°F (11.1°C) and 32°F (0°C). After the pelletization, the IV of Polymer A changed very little. The IVs, pellet sizes, densities, and crystallinities (by density) of the pelletized polymers obtained are listed in the'following table:
Table 1 (Table Removed)

The density and crystallinity of the pelletized polymer increased slightly with increasing quenching water temperature. This is because the quenching rate of the PTT melt strand is slower with warmer quenching water, allowing the polymer to crystallize to a greater extent before it is cooled to below its Tg.
Each of the 3 pelletized polymers was crystallized and dried at 170°C for 4 hours in a small-scale SSP reactor as described in the procedure for the SSP experiments. About 50 grams of polymer was used in each crystallization/drying run. During the first 15 minutes, a high enough nitrogen flow was used to fluidize the polymer bed. Then the nitrogen flow was reduced to 18 SCFH (509.7 litres per hour) to maintain a static bed for the remaining portion of the run. Samples were taken 0.25, 0.5, 1, and 2 hours after the .beginning of each run and at the end of each run. The IV of each polymer did not change significantly during the run. Note that crystallization and drying (for melt processing) of PTT requires 15 to 30 minutes and about 4 hours respectively.
The samples taken during the crystallization/crying runs as well as the amorphous pelletized polymers (0-hour samples) were subjected to the friability test. The results are shown in the following table:
Table 2
Percent Failure Rates of Friability Tests for Crystallized/Dried
Samples of Pelletized PTT
(Table Removed)
All the amorphous pellets of the pelletized polymers were somewhat flattened without being broken after the tests. However, all the polymers were embrittled to various extents after being crystallized and dried for various periods of time. The longer the crystallization/drying time (or the higher the crystallinity), the more brittle the polymers became. It can also be seen that the degrees of embrittlement were higher with the lower molecular weight polymers. The above observations are in agreement with the classic polymer crystallization theory. What is not expected is the fact that the friability of the crystallised/dried PTT after a fixed time of crystallization/drying decreased with decreasing quenching water temperature used in pelletizing the polymer. This can not be explained by, and, in fact, is contrary to the conventional polymer crystallization theory.
Since the PTT melt strands cool very rapidly during pelletizing, practically all the crystallization of PTT takes place near its Tg (about 45°C). Crystallization of polymers involves two consecutive processes: the formation of nuclei and their subsequent growth. Because lower temperatures favour nucleation while higher temperatures favour spherulitic growth, crystallization of PTT during pelletizing produces large numbers of nuclei and tiny crystallites and a small difference in crystallinity can mean a great difference in numbers of nuclei and tiny crystallites formed. This is supported by the fact that clear PTT (PTT that does not contain Tio2) pelletized in a conventional pelletizing system
remains transparent even though it may have about 15 % crystallinity because the crystallites are small enough not to scatter visible light. During crystallization at
170°C, the temperature of the polymer is raised rapidly and the existing nuclei and tiny crystallites grow into spherulites with very few new nuclei being created. Therefore, a greater number of smaller spherulites will be formed in a pelletized polymer with a higher existing crystallinity, i.e. one pelletized with a warmer quenching water. The classic polymer crystallization theory predicts the brittleness of crystallised polymer increases with increasing spherulite size as well as crystallinity, contrary to the friability test results in the table above.
Thus, it has been unexpectedly discovered that the friability of crystallized PTT pellets can be reduced or the robustness of crystallized PTT pellets can be increased by decreasing the temperature of the quenching water used to pelletize the polymer from the melt polymerization reactor. The use of colder quenching water improves the quenching rate of the melt strands, thereby lowering the polymer temperature to below its Tg in a shorter time. One way to decrease the quenching water temperature is by adding a lower temperature heat exchanger downstream of the normal heat exchanger used in the conventional pelletizing system to cool the recycled quenching water. The coolant for the lower temperature heat exchanger (referred to as brine, an aqueous solution of glycol or salt) can be supplied by a chiller. 3y using such an additional lower temperature heat exchanger," it is possible to cool the recycled quenching water to below room temperature (i.e. about 77°F or 25°C). Of course, the quenching rate of the melt strands can be further increased by increasing the flow race of the quenching water.
Example 7
A delustered PTT resin with an IV of 0.653 dl/g (referred to as Polymer C) produced in a batch polymerization plant was p'elletized using quenching water temperatures of 100, 74, 53, and 32°F (37.8, 23.3, 11.7, and 0°C) to prepare prepolymers for SSP experiments. The IVs, pellet sizes, polymer densities, and crystallinities of the pelletized polymers obtained are listed in the following table:
Table 3 (Table Removed)

The IV changes during the pelletizations were insignificant. The density and crystallinity of the pelletized prepolymer increased slightly with increasing quenching water temperature.
The pelletized polymers thus obtained were solid state polymerized at 210°C for 22 hours. Samples were taken at various intervals during each of the SSP runs. These samples were tested for IV and density. From the density data, the crystallinities were calculated for all the samples. Additionally, all of these samples were subjected to the friability test to compare their relative friabilities. The test results are listed in Table I.
Table I Experimental Results for Example 5
(Table Removed)
It can be seen in Table I that each prepolymer was very friable (with 100% or 95% friability-test failure rate) at the beginning of the SSP step (after the crystallization/drying step) and gradually became less
friable as the SSP time was increased. The results in Table I also indicates that the TVs and the crystallinities of the four prepolymers increased with increasing SSP time as expected, but the quench water temperature had little effects on the IV and the crystallinity after each period of SSP. Since the crystallinity increased with increasing SSP time and the conventional polymer crystallisation theory predicts that polymer becomes more brittle as the crystallinity is increased, this observation is contrary to the conventional polymer crystallization theory. It is believed that the reduction in the pellet friability by SSP is a result of the increase in the molecular weight. During the course of SSP, most of the polymer chain ends are forced out of the crystallites into the amorphous regions between the crystallites, as a result of continued perfection of the crystalline structure. The reactions between these chain ends form tie-molecules between crystallites, thereby strengthening the polymer.
Since the increase in the robustness of the PTT pellets is mainly due to the increase in the IV, the failure rates are plotted against the IV in Figure 1 for each of these prepolymers, which were pelletized with various quenching water temperatures. It is obvious from this figure that the friability of the solid stated product of each fixed IV decreases with decreasing quenching water temperature used to pelletize the prepolymer. This is also contrary to the conventional theory of polymer crystallization, which predicts that the friability of a crystalline polymer increases with increasing spherulite size. Since a prepolymer pelletized with a lower quenching water temperature will have a smaller number of nuclei or tiny crystallites, and since
the quenching, water temperature does not significantly affect the crystallinity of the solid stated product with a fixed IV, the spherulites formed within the solid stated product of this prepolymer will be larger. It is theorised that as the average size of the spherulites is increased, the perfection of the crystalline structure becomes more advanced and more chain ends will be concentrated in the amorphous regions just outside the spherulites. Furthermore, as the spherulites grow larger, the boundaries of the adjacent spherulites get closer. As a result, more tie-molecules will be formed between spherulites to strengthen the polymer structure.
This example demonstrates that the friability of solid stated PTT can be effectively reduced by lowering the temperature of the quenching water used in the pelletizing of the prepolymer. Example 6
Prepolymer C-53 prepared in Example 5 was solid state polymerized in a small SSP reactor at 190, 200, 210, and 220°C. The samples taken during these four SSP runs were characterized for IV, density, and crystallinity and subjected to the friability test.
Table II lists the test results.
Table II Experimental Results for Examp'e 6
(Table Removed)

The crystal Unity data in Table II are plotted against the SSP time in Figure 2. This figure indicates that the crystallinity after each period of SSP time increases with increasing SSP temperature. Furthermore, because higher temperatures favour spherulitic growth, the spherulite size of the solid stated polymer should also increase with increasing SSP temperature.
The friability test failure rate data in Table II are plotted against the IV in Figure 3. It can be seen that the friability of the solid stated product with a fixed IV decreases with increasing SSP temperature. Since solid stated products prepared at higher temperatures have higher crystallinities with larger sphemlites, this observation is also opposite to the conventional polymer crystallization theory, which asserts that the brittleness of a crystalline polymer increases with increasing crystallinity and spherulite size. Thus increasing SSP temperature is another unexpected method that can effectively increase the robustness cf solid stated PTT pellets. Example 7
A delustered PTT resin with an IV of 0.545 dl/g (referred to as Polymer D) produced in a batch polymerisation plant was pelletised with various quenching water temperatures. The IVs, pellet sizes, polymer densities, and crystallinities of these pelletized prepolymers are listed in Table 4.
Table 4 (Table Removed)

All of these palletized prepolymers were solid state polymerized at 210°C. The samples taken during the SSP runs were characterized for IV, density, and crystallinity. Furthermore, these samples were subjected to the friability test. The test results are listed in Table III. The friability test failure rates are plotted against the IV for these SSP runs in Figure 4. This figure also shows that the friability of the solid stated product of 0.545 dl/g IV PTT prepolymer decreases pronouncedly with decreasing quenching water temperature used in the pelletizing of the prepolymer.
Table III Experimental
Results for Examole 7 (Table Removed)

Example 8
Prepolymer D-52 prepared in Example 7 was solid state polymerized at 190, 200, 210, 220, and 225°C in a small-scale laboratory SSP reactor. The samples taken during these SSP runs were characterized for IV and density and subjected to the friability test. The test results are shown in Table IV. The friability test failure rates are plotted against the IV for these SSP runs in Figure 5. It can be seen in this figure that the friability of the solid stated product of 0.545 dl/g IV prepolymer also decreases pronouncedly with increasing SSP temperature.
Table IV ExDerimental
Results for Examnle R
(Table Removed)

Since the SSP in commercial production is terminated when the desired product IV is reached, we are most interested in the friability at the product IV. The friability test failure rates for solid stated products at various IVs prepared with various prepolymers at various SSP temperatures can be estimated from Figures 1, 3, 4, and 5. Thus, the friability test failure rates of solid stated products with IVs of 0.88 and 0.92 dl/g prepared with various prepolymers at various SSP temperatures are compared in Table 5.
Table 5 (Table Removed)


It can be seen in this table that, in addition to the prepolymer pelletizing quenching water temperature and the SSP temperature, the required IV lift in the SSP (AIV) also has a significant effect on the friability of the solid stated product. The greater the IV lift, the lower the friability of the solid stated product. Thus yet another way has been discovered to reduce the friability of solid stated PTT, i.e. by increasing the IV lift in the SSP. Preferably, the required IV lift' can be increased by using a prepolymer with a lower IV. Alternately, the IV lift can be increased by increasing the product IV, provided a higher product IV is suitable for the intended application.





We claim:
1. A method for producing polytrimethylene terephthalate which comprises polycondensation of 1,3-propane diol and dimethylterephthalate or terephthalic acid followed by solid state polymerization of the polycondensation reaction product to increase the intrinsic viscosity, which comprises quenching the solid state polymerization product in water at a temperature of from 0 to 18°C followed by pelletization of the quenched product.
2. A method as claimed in claim 1 wherein the polycondensation is carried out such that the polycondensation reaction product has an intrinsic viscosity of from 0.35 to 0.70 dl/g. The method as claimed in claims 1 or 2 wherein the solid state polymerization is carried out such that the solid state polymerization product has an intrinsic viscosity of from 0.80 to 2 dl/g

Documents:

1986-DELNP-2003-Abstract-(29-05-2009).pdf

1986-delnp-2003-abstract.pdf

1986-DELNP-2003-Claims-(29-05-2009).pdf

1986-DELNP-2003-Claims-(30-09-2009).pdf

1986-delnp-2003-claims.pdf

1986-delnp-2003-correspondence-others -(30-09-2009).pdf

1986-DELNP-2003-Correspondence-Others(30-09-2009).pdf

1986-DELNP-2003-Correspondence-Others-(29-05-2009).pdf

1986-DELNP-2003-Correspondence-Others-(30-09-2009).pdf

1986-delnp-2003-correspondence-others.pdf

1986-delnp-2003-description (complete).pdf

1986-DELNP-2003-Drawings-(29-05-2009).pdf

1986-delnp-2003-drawings.pdf

1986-DELNP-2003-Form-1-(29-05-2009).pdf

1986-DELNP-2003-Form-1-(30-09-2009).pdf

1986-delnp-2003-form-1.pdf

1986-delnp-2003-form-18.pdf

1986-DELNP-2003-Form-2-(29-05-2009).pdf

1986-delnp-2003-form-2.pdf

1986-DELNP-2003-Form-3-(29-05-2009).pdf

1986-DELNP-2003-Form-3-(30-09-2009).pdf

1986-delnp-2003-form-3.pdf

1986-DELNP-2003-Form-5-(29-05-2009).pdf

1986-DELNP-2003-Form-5-(30-09-2009).pdf

1986-delnp-2003-form-5.pdf

1986-DELNP-2003-GPA-(29-05-2009).pdf

1986-DELNP-2003-PA-(29-05-2009).pdf

1986-delnp-2003-pa.pdf

1986-delnp-2003-pct-101.pdf

1986-delnp-2003-pct-210.pdf

1986-delnp-2003-pct-409.pdf

1986-delnp-2003-pct-416.pdf

1986-DELNP-2003-Petition-138(30-09-2009).pdf

1986-DELNP-2003-Petition-138-(30-09-2009).pdf

abstract.jpg


Patent Number 244041
Indian Patent Application Number 1986/DELNP/2003
PG Journal Number 47/2010
Publication Date 19-Nov-2010
Grant Date 16-Nov-2010
Date of Filing 21-Nov-2003
Name of Patentee SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Applicant Address CAREL VAN BYLANDTLAAN 30, NL-2596 HR THE HAGUE, THE NETHERLANDS.
Inventors:
# Inventor's Name Inventor's Address
1 BLACKBOURN ROBERT LAWRENCE 16410 BATTLECREEK DRIVE, HOUSTON, TX 77095, U.S.A.
2 DUH BEN. 768 JENNIFER TRAIL, TALLMADGE, OH 44278, U.A.S.
3 KIIBLER KATHLEEN SUZANNE. 22815 BUCKTROUT LANE, KATY, TX 77449, U.S.A.
4 TSE CECILIA ZUQI 22415 BELLOWS BEND DRIVE, KATY, TX 77450, U.S.A.
PCT International Classification Number C08G 63/80
PCT International Application Number PCT/EP2002/05978
PCT International Filing date 2002-05-30
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/295,273 2001-06-01 U.S.A.