Title of Invention

A METHOD OF MAKING RAPIDLY CRYSTALLIZABLE AMORPHOUS POLYETHYLENE NAPHTHALATE POLYMER

Abstract The invention relates to modified Polyethylene Naphthalate (PEN) polymers with fast crystallizing properties, which helps in crystallization of amorphous PEN resin prior to its solid state polymerization (SSP).
Full Text FORM-2
THE PATENT ACT, 1970
(39 of 1970)
&
THE PATENT RULES, 2003
COMPLETE SPECIFICATION
(See section 10 and Rule 13)
"FAST CRYSTALLIZING MODIFIED POLYETHYLENE NAPHTHALATE"
FUTURA POLYESTERS LIMITED
An Indian Company
of Paragon Condominium, 3 rd Floor, Pandurang Budhakar Marg,
Mumbai-400 013, Maharashtra, India.
THE FOLLOWING SPECIFICATION PARTICULARLY DESCRIBES THE INVENTION AND THE MANNER IN WHICH IT IS TO BE PERFORMED.

FAST CRYSTALLIZING MODIFIED POLYETHYLENE NAPHTHALATE
Related Applications
This application claims the benefit of Indian Provisional Application Serial No.
248/MUM/2006, filed on February 21, 2006, which is hereby incorporated by reference in its entirety.
Field of the Invention
The invention relates to a modified Polyethylene Naphthalate (PEN) polymers.
What is envisaged in accordance with this invention is a modified Polyethylene Naphthalate (PEN) polymer with fast crystallizing properties, which helps in crystallization of amorphous PEN resin prior to its solid state polymerization (SSP).
Background of the Invention
Polyethylene naphthalate (PEN) is a naphthalate-based polyester that is used in the production of fiber, film and rigid packaging applications. Like most thermoplastic polyesters, PEN is also produced by melt phase polymerization, which gives the amorphous polymer a medium intrinsic viscosity (I.V.). To increase the I.V., amorphous PEN chips are crystallized and then subjected to SSP. The pre-crystallization process used for the related polyester polyethylene terephthalate (PET) cannot be used for PEN because of the differences in their physical and chemical properties. For example, PEN's Tg is about 120 °C, its melting point, Tm, is about 270 °C, and its softening point or sticking temperature is in the range of about 140 °C to about 150 °C. Hence, the crystallization temperature used for PEN is normally in the range of about 180 °C to about 220 °C, which is much higher than that used for PET. In this crystallization process, PEN chips should undergo a sticky stage when it crosses the softening point or sticking temperature. To avoid sticking or lumping of PEN chips, agitated vessels or fluidized beds are used.
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Several methods have been adopted to precrystallize amorphous PEN before it is subjected to SSP.
US 4,798,883 describes a modified PEN process with enhanced crystallization characteristics of amorphous PEN by the addition of small amount of polyether glycols such as polytetramethylene glycol and polyethylene glycol.
US 4,963,644 describes precrystallization of amorphous PEN prepolymer which comprises: (1) heating the amorphous PEN prepolymer to a temperature that is within the range of about 80 °C to about 140 °C in the presence of a stream of an inert gas or under a vacuum to devolatilize the amorphous PEN prepolymer; and (2) subsequently heating the devolatilized PEN prepolymer to a temperature within the range of about 150 °C to about 260 °C while providing agitation to produce crystallized PEN prepolymer. The precrystallized PEN prepolymer is subsequently subjected to SSP by heating it to a temperature of about 50 °C to about 1 °C below its sticking temperature for a period of time sufficient to produce the high molecular weight PEN resin.
US 5,412,063 describes the manufacture of PET and PEN chips wherein the amorphous strands have a hole in the middle. The chips do not need any special precrystallization procedure, such as devolatilization, prior to SSP.
US 5,523,361 describes a precrystallization procedure for PEN involving coating the amorphous PEN chips with ethylene carbonate, which avoids the devolatilization procedure before SSP.
US 5,744,578 and 5,750,644 describe processes for the crystallization of a PEN prepolymer containing volatile components. The temperature is maintained in the range of about 20 °C above the Tg and about 10 °C below the Tm while the PEN prepolymer is agitated. The PEN prepolymer is present as chips or pellets. The crystallization is performed in the presence of a liquid or a mixture of liquids that do not degrade the polymer during crystallization. The liquid or liquids employed may be those whose
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vapor pressure at the amorphous PEN softening temperature is insufficient to forestall expansion of the pellets. When this class of liquid or liquids is employed, the crystallization vessel is pressurized with an inert gas, including air, to prevent prepolymer expansion. If the liquid or liquids possess sufficiently high vapor pressures at the PEN softening temperature, the pellets do not expand even without the inert air pressurization, thereby avoiding deformation of the PEN chips during crystallization.
US 6,124,423 describes a PEN copolymer process wherein the devolatilization prior to SSP can be avoided by modifying the PEN with diethylene glycol (DEG). Crystallizing the PEN copolymer solids by heating the solids to at least their sticking temperature at an average rate of at least 10°C /minute, to form agglomerate-free crystallized solids. The process may be performed under agitation. The pellets heated up during the crystallization step do not agglomerate or suddenly expand as the temperature rises to and through the sticking temperature of the PEN copolymers. The process allows one to rapidly heat up PEN during crystallization, and do so without conducting a prior drying step or devolatilization step.
All the above precrystallization procedures prior to SSP are cumbersome and involve invariably more than one stage of precrystallization, thereby risking deterioration in quality.
A need therefore exists for a simpler crystallization procedure that uses only a single stage of crystallization.
Summary of the Invention
The present invention provides processes for making amorphous polyethylene naphthalate (PEN) polymer by melt phase polymerization and the crystallization of the amorphous PEN in a single stage.
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In one aspect, the invention provides a rapidly crystallized amorphous polyethylene naphthalate (PEN) polymer comprising an I.V. of about 0.6 dL/g with a carboxyl end group number of about 18 meq/kg and a Teh of about 195 °C.
I.V. represents Intrinsic Viscosity which is easily measured by solution viscosity using the Ubbellode viscometers.The I.V. is directly related to the Molecular Weight through known equations. Higher the I.V means higher MW. One normally gets upto a certain lower I.V. in melt polymerization e.g. approx. 0.5 with PEN which is increased to about 1.0 I.V. by SSP as high MW is required for applications like tire cord.
A COOH No. of about 1& for the PEN in accordance with this invention is considerably lower than for ordinary PEN ( about 25 - 30). Generally higher COOH No. promotes more degradation in the polymer while processing and this lower COOH No. gives more thermal stability to the PEN in its subsequent processing.
Teh is the accepted terminology which indicates peak temp, of crystallization as measured by DSC thermal analyzer. This temp, is always measured during the second heating cycle wherein the previous thermal history of the sample is totally erased. After the first heating cycle the polymer is taken well above its melting point to destroy any crystatllites and immediately quenched to ambient to get a perfect amorphous sample. This is again heated at a programmed rate in the 2nd heating cycle which gives the Teh value. A lower value indicates that the material has fast crystallizing property induced by the nucleating agents as observed in the PEN in accordance with this invention. This fast crystallizing PEN with lower Teh value is reflected as an advantage when the material is converted for e.g. to tire cord. During the tire cord spinning the drawn filaments have to be heat set at a higher temperature to impart high tenacity and high modulus for which crystallization is a prerequisite. Since the filaments are taken through a high temperature zone, due to its fast crystallizing nature the desired properties in the tire cord filament is easily obtained.
In another aspect, the invention provides methods of making a polyethylene naphthalate (PEN) polymer that rapidly crystallizes. The method comprises the steps of: (a)
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transesterifying dimethyl 2,6-naphthalene dicarboxylate (NDC) in the presence of (i) monoethylene glycol (MEG); (ii) at least one transesterification catalyst; and (iii) at least one nucleating agent, wherein about 80% of the transesterifying step is carried out at about 1050 mbar followed by about 20% of the transesterifying step being carried out at about 500 mbar, to form a prepolymer; and (b) polymerizing the prepolymer at about 250 °C to about 305 °C in the presence of a polymerization catalyst and at least one thermal stabilizer. The molar ratio of NDC:MEG is about 1:1.5 to about 1:2.5, preferably about 1:1.5 to about 1:2.1.
In an embodiment, the transesterifying step is carried out by progressively increasing the temperature from about 140 °C to about 255 °C for about 180 minutes to about 300 minutes.
The transesterification catalyst is an element selected from a group consisting of manganese, calcium, zinc, cobalt, antimony, titanium, tin, or a combination thereof.
Nucleating agents are also added to increase the rate of crystallization of the amorphous PEN. The nucleating agent is selected from a group consisting of a sodium compound, a sorbitol, and a nano particle containing compound.
In an embodiment, the transesterifying step further comprises the addition of a color agent, such as a cobalt compound.
In an embodiment, the polymerizing step is carried out at about 240 °C to about 285 °C in the initial stage of the reaction and about 285 °C to about 305 °C in the later stage of the reaction at a pressure of about 2 mbar to complete vacuum. These results in faster I.V. build up, and lower melt viscosity, for easy removal from the reactor in a shorter time, preventing degradation and controlling color.
The polymerization catalyst is a compound comprising antimony, titanium, tin, or a combination thereof.
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The thermal stabilizer is Triethylphosphonoacetate (TEPA), orthophosphoric acid (OPA), or a combination thereof.
In another embodiment of the method of the invention, Ethylene acrylic acid sodium ionomer is added as a nucleating agent after polymerization.
In another embodiment, a thermal stabilizer is added after the transesterifying step.
The methods of the invention further comprise the step of extruding the PEN melt into strands in water and then cutting them into chips.
Prior to Solid State Polymerization, the amorphous PEN chips are crystallized by a unique and simple single stage process. This crystallization procedure does not require a devolatilization step as described in prior art patents. Due to the presence of nucleating agents, a single stage crystallization can be done at a higher temperature between about 190°C and about 230 °C, compared to the usual temperature of less than 160 °C when devolatilization is required. In another embodiment, the methods of the invention comprise placing chips in a fluidized bed crystallizer at about 190 °C to about 230 °C to form precrystallized chips.
In another embodiment, the methods of the invention further comprise the step of subjecting the precrystallized chips to solid state polymerization (SSP) at about 240 °C to about 260 °C initially in the presence of nitrogen, say for 3 - 5 hours, then releasing Nitrogen pressure gradually and maintaining fine vacuum till required I.V. is attained.
In another aspect, the methods of the invention provide an amorphous polyethylene naphthalate (PEN) polymer.
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Brief Description of the Drawings
The foregoing and other objects, features and advantages of the present invention, as
well as the invention itself, will be more fully understood from the following description
of preferred embodiments when read together with the accompanying drawings, in which:
Figures 1A and IB provide front views of a precrystallizer and modified precrystallizer for precrystallization of the PEN resin of the invention.
Figures 2A and 2B provide lateral views of a precrystallizer and modified precrystallizer for precrystallization of me PEN resin of the invention.
Figures 3A and 3B provide top views of a precrystallizer and modified precrystallizer for precrystallization of the PEN resin of the invention.
Referring to the drawings, in the figures the following reference numerals refer to the designated part:
1 - Amorphous chips inlet port, 2 - Amorphous chips outlet port
3 - Inert gas inlet valve 4 - Inert gas outlet nozzle
5 - Vertical baffles
In use, the amorphous chips are charged into the fluid bed pre-crystallizer through the chips inlet port (1). An inert hot gas, preferably Nitrogen is passed from the bottom valve (3) and vented off from the top of the crystallizer via nozzle (4). The precrystallizer is divided by vertical baffles (5). Pre-crystallized chips are collected from chips outlet port (2).
Hot nitrogen gas is distributed through out the pre-crystallizer, this helps in carrying the chips through various baffles. The vertical baffles maintain a continuous flow and controls the residence time of the chips. The gas from the outlet nozzle is send to suction pump where it is reheated and send back to the pre-crystallizer.
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The nitrogen pressure is maintained at about 0.1 bar and temperature at about 215 — 230°C. The residence time of the amorphous chips in the crystallizer is about 20 - 40 minutes.
The modified pre-crystallizer, in accordance with this invention, has the amorphous chips inlet port at the top. This modification increases the distance between the fluid-bed and chips, this in turn increases the exposure time of chips to hot gas.
Detailed Description of the Invention
The invention provides compositions of and methods of making a polyethylene naphthalate (PEN) polymer that rapidly crystallizes. The method comprises the steps of: (a) transesterifying dimethyl 2,6-naphthalene dicarboxylate (NDC) in the presence
of (i) monoethylene glycol (MEG); (ii) at least one transesterification catalyst; and (iii) at least one nucleating agent, wherein about 80% of the transesterifying step is carried out at about 1050 mbar followed by about 20% of the transesterifying step being carried out at about 500 mbar, to form a prepolymer; and (b) polymerizing the prepolymer at about 250 °C to about 305 °C in the presence of a polymerization catalyst and at least one thermal stabilizer. The molar ratio of NDC:MEG is about 1:1.5 to about 1:2.5, preferably about 1:1.5 to about 1:2.1.
In an embodiment, the transesterifying step is carried out by progressively increasing the temperature from about 140 °C to about 255 °C. In another embodiment, about 80% of the transesterifying step is carried out at atmospheric pressure. In another embodiment, about 20% of transesterifying step is carried out by decreasing the pressure to about 500 mbar. In another embodiment, about 80% of the transesterifying step is carried out at about 1050 mbar followed by about 20% of the transesterifying step being carried out at about 500 mbar at a temperature of about 230 °C to about 255°C. The transesterifying step is carried out for about 180 minutes to about 300 minutes.
In an embodiment, the transesterification catalyst is selected from the group consisting of manganese acetate, titanium acetate, calcium acetate, zinc acetate, antimony trioxide,
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I

antimony triacetate, cobalt acetate, tin oxide, and a combination thereof. Manganese acetate (as Mn) is added at about 30 ppm to about 200 ppm, preferably about 35 ppm to about 150 ppm.
In an embodiment, the transesterification catalyst is added at the start of the transesterifying step. In another embodiment, a portion of the transesterification catalyst is added at the start of the transesterifying step and the remaining portion in the
middle of the transesterifying step. In an embodiment of the invention, methanol is removed during the transesterifying step.
The nucleating agent may be sodium acetate, sodium benzoate, nano clay, nano particles, micronized sorbitol, sodium salicylates, nyacol, sodium sorbitrate, nano silica, tungsten trioxide, 3,5-di-f-butyl-4-hydroxyphenyl propionic acid methyl ester, ethylene acrylic acid sodium ionomer, or a combination thereof. NYACOL is an amorphous nano particle (mean particle size is 50 nm) silica additive dispersed at 30% as its oxide in Ethylene Glycol.
The nucleating agent is generally added in the range of about 10 ppm to about 4000 ppm. Sodium acetate is added at about 2 ppm to about 200 ppm, preferably about 10 ppm to about 150 ppm. Sodium benzoate is added at about 100 ppm to about 1000 ppm, preferably about 200 ppm to about 800 ppm. Nano clay is added at about 100 ppm to about 3000 ppm. Nyacol is added at about 1000 ppm to about 4000 ppm, preferably about 2500 ppm to about 3000 ppm.
In an embodiment, the transesterifying step further comprises the addition of a color agent, such as cobalt acetate, 8,9,10,1 l-Tetrachloro-12H-phthaloperin-12-one (Red Toner), l,4-Bis(mesitylamino)anthraquinone (Blue Toner), or a combination thereof. The cobalt compound is added as Co at about 10 ppm to about 80 ppm, preferably about 20 ppm to about 60 ppm.
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In an embodiment, the polymerizing step is carried out at about 285 °C in the initial stage of the reaction and at about 300 °C to about 305 °C at a later stage of the reaction at about 2 mbar to complete vacuum. The initial stage is about 40 minutes to about 70 minutes. The final stage is about 15 minutes to about 30 minutes. In another embodiment, the polymerizing step is carried out by gradually increasing the temperature from about 250 °C to about 305 °C and decreasing the pressure from about 500 mbar to about 2 mbar. In an embodiment, the polymerizing cycle is carried out for about 55 minutes to about 100 minutes, preferably about 100 minutes.
The polymerization catalyst is antimony trioxide, tetra-n-butyl titanate (TnBT), butylstannoic acid, or a combination thereof. Antimony trioxide (as Sb) is added at about 150 ppm to about 300 ppm, preferably about 180 ppm to about 250 ppm. In another embodiment, antimony, germanium, titanium and tin are added as polymerization catalysts.
The thermal stabilizer is Triethylphosphonoacetate (TEPA), orthophosphoric acid (OPA), or a combination thereof. In an embodiment, the thermal stabilizer is added after the transesterifying step. The thermal stabilizer is added at about 40 ppm to about 200 ppm, preferably about 60 ppm to about 150 ppm.
In another embodiment of the methods of the invention, Aclyn 285 [Ethylene Acrylic Acid Sodium Ionomer product] is added as a nucleating agent after polymerization. The methods of the invention further comprise the step of extruding the PEN melt into strands in water and then cutting them into chips.
Due to the presence of nucleating agents, a single stage crystallization can be done at a higher temperature between about 190 °C and about 230 °C, compared to the usual temperature of less than 160 °C for methods involving devolatilization. In an embodiment of the invention, the fast crystallizing amorphous PEN chips are charged into a top entry (Figure 1) or modified top entry fluid bed crystallizer, which operates
with a stream of air / nitrogen heated to a temperature of between about 190 °C and
about 230 °C to form precrystallized chips. The Fluid Bed-Crystallizer was supplied
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by SINCO Engineering S.P.A, Tortona, Italy. This was further modified in-house by the applicant.
Referring to Figure 2, the modified top entry fluid bed crystallizer differs from the top entry design in that it increases the residence time of the amorphous PEN chips before it reaches the bed such that the PEN becomes crystalline faster, compared to the conventional side entry crystallizers. This modification in the entry port increases the distance between the chips and the fluid bed, which in turn increases the exposure of chips to hot gas. The time taken for pre-crystallizing the chips in an improved Fluid Bed Crystallizer is around 40 minutes, whereas the devolatilization process consumes about 10 hours. Thus improved Fluid Bed Crystallizer saves time and energy consumption. Due to this prior crystallization, the SSP can be done at higher temperatures without the problem of sticking or lumping thus eliminating the lengthy devolatilization step.
In another embodiment, the methods of the invention further comprise the step of subjecting the precrystallized chips to solid state polymerization (SSP) at about 240 °C to about 260 °C initially in the presence of nitrogen, say for 3 - 5 hours, then releasing Nitrogen pressure gradually and maintaining fine vacuum till required I.V. is attained.
Practice of the invention will be still more fully understood from the following examples, which are presented herein for illustration only and should not be construed as limiting the invention in any way.
Exemplification-
Example 1
Dimethyl 2,6-naphthalene dicarboxylate (NDC) and Monoethylene Glycol (MEG) are taken in 1:1.75 molar ratio. 14 kg of NDC and 7 kg of MEG are added to a batch reactor. To this mixture, 75 ppm sodium acetate, 300 ppm sodium benzoate, and 3000 ppm of nano clay are added as nucleating agents, 100 ppm manganese acetate is added as an ester interchange catalyst, and 25 ppm cobalt acetate is added as colorant. Esterification is carried out by progressively increasing the temperature to 225 °C and
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decreasing the pressure from 1050 mbar to about 500 mbar for 200 minutes, while simultaneously removing the by-product methanol. 80% of the transesterifying step is carried out at about 1050 mbar followed by 20% of the transesterifying step being carried out at about 500 mbar. After esterification, 100 ppm triethylphosphono acetate is added as a heat stabilizer and 250 ppm antimony trioxide (Sb2(>3) is added as a polymerization catalyst and polymerization is conducted under progressive vacuum, say from 500 - 2 mbar for 45 minutes, increasing the temperature from about 250 °C to about 305 °C within that 45 minutes to create an amorphous PEN melt. The residence time of the PEN melt at 305 °C is kept brief, say 35 minutes, in order to minimize degradation of the PEN melt while simultaneously take advantage of the increased rate of polymerization at this high temperature. The amorphous PEN melt is then extruded as a strand and cut into chips according to standard methods. The amorphous chips are then crystallized in a modified fluid bed crystallizer which has an inlet at the top rather than in the side, this modification increases the distance between the chips and the fluid bed, this in turn increases the exposure time of chips to hot gas. The amorphous chips are then crystallized by subjecting them to a temperature of about 225 °C in 0.1 bar nitrogen pressure for about 30 minutes. The crystallized chips are then subjected to SSP in a batch reactor by heating to about 260 °C for about 30 hours to increase the I.V. of about 1.0 dL/g
The following table provides properties of the amorphous and SSP PEN resin modified with nucleating agents.
TABLE 1 Important characteristics of the PEN polymer of Example 1

I.V.(dL/g) L* CIE Lab a* CIE Lab b* CIE Lab COOHNo.meq/kg DEG(%) Tg°C Tm°C lCe°c Tch°c
AMORPHOUSPEN -0.56 68.1 -1.2 -3.3 27.0 0.79 123.8 266.2 127.2 195
SSP PEN 1.06 78.2 -2.0 6.8 - - - - - -
Tg= glass transition temperature; Tm = melting point; Tcc = crystallization temperature
while cooling from the melt; Tch = crystallization temperature during the 2nd heating cycle
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Example 2
A 1:2 molar ratio of NDC:MEG, viz.7.1 Kg of Dimethyl 2,6-naphthalene dicarboxylate and 4.0 Kg of Monoethylene glycol are taken in a batch reactor. 3.7 g of Manganese acetate is added in two equal parts (40 ppm + 40 ppm as Mn), one part before esterification and other part at the mid of esterification, say after 30 % distillation of methanol and 0.02 g each of colorants like RT and BT (2.5 ppm) are added to the batch reactor. Esterification is carried out by increasing the temperature to about 255 °C, decreasing the pressure to 750 mbar and simultaneously removing the by-product. 80% of the transesterifying step is carried out at about 1050 mbar followed by 20% of the transesterifying step being carried out at about 750 mbar The process time for esterification is about 260 minutes.
After esterification, 2.4 g of polymerization catalyst Antimony trioxide (200 ppm as Sb), 5.07 g (100 ppm as P) of triethylphosphono acetate is added. Polymerization is conducted at about 250 °C to about 305 °C under vacuum for about 90 minutes in two stages. In the initial stage the temperature is raised from 250 - 285 °C for 70 minutes and in the final stage the temperature is raised from 285-305 °C for 20 minutes. Both the stages are carried out in complete vacuum. The residence time of the PEN melt at 305 °C is maintained to be minimum. The amorphous melt of PEN is then extruded as a strand and cut into chips.
The amorphous chips are then crystallized in the modified fluid bed crystallizer, which has an inlet at the top rather than in the side, which increases the distance between the chips and the fluid bed, which in turn increases the exposure of chips to hot gas. The crystallizer is fed at about 215 °C. Thus a devolatilization process is avoided.
The crystallized chips are then subjected to SSP in a batch reactor by heating to 260 °C
initially in the presence of nitrogen, say for 4 hours, then release Nitrogen pressure gradually and maintain fine vacuum to increase the IV.
Example 3
The resin composition is similar to example.2 except for the addition of nucleating
agent Nyacol, (Nanotechnologies Inc., USA) (28 g, 2800 ppm) before esterification in
the reactor. Esterification and polymerization are carried out under similar temperature and pressure. The total time taken for esterification is 260 minutes and polymerization is
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85 min. The amorphous polymer is extruded under nitrogen pressure and collected as pellets.
Example 4
The resin composition is similar to example.2 except for the addition of nucleating agent Sodium benzoate (4 g, 400 ppm) before esterification in the reactor. Esterification and polymerization are carried out under similar temperature and pressure. The total time taken for esterification is 260 minutes and polymerization is 90 min. The amorphous polymer is extruded under nitrogen pressure and collected as pellets.
Example 5
A 1:1.75 molar ratio of NDC and MEG, say, 14 Kg of Dimethyl 2,6-naphthalene dicarboxylate and 7 Kg of Monoethylene glycol are mixed in a esterification reactor. 2.6 g of Manganese acetate (20 ppm and 20 ppm as Mn), 0.2 g each of colorants like RT and BT (1.5 ppm as such, each) and 1.2 g of Cobalt acetate (20 ppm as Co) colorant are added to the above said mixture. The esterification reaction is carried out at about 245 °C for about 220 minutes in a pressure of about 500 mbar. 80% of the transesterifying step is carried out at about 1050 mbar followed by 20% of the transesterifying step being carried out at about 500 mbar
After esterification, 4.01 g of Sb2C>3 (220 ppm as Sb), 15.2 g (150 ppm as P) of thermal stabilizier Triethylphosphono acetate (TEPA) and 3.7 g (150 ppm as Sn) polymerization catalyst butylstannoic acid are added. Polymerization is conducted at about 250 to about 305 °C under vacuum for about 70 minutes in two stages as mentioned in example. 2. After reaching the required molecular weight, about 1800 ppm of Aclyn 285 (25.2 g) from Honeywell, USA is added and allowed to interact with the melt at about 305 °C with a pressure of about 1 mbar for about 20 minutes. The amorphous melt of PEN is then extruded out as a strand and cut into chips.
The amorphous chips are then crystallized in the improved fluid bed crystallizer by subjecting it to 225 °C. The crystallized chips are then subjected to SSP at about 260
°C initially in the presence of nitrogen, say for 4 hours, then release Nitrogen pressure gradually and maintain fine vacuum till required I.V. is attained, bypassing the devolatilization process.
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Table-II Resin composition in the Examples

Ingredients Example 1 Example2 Example3 Example 4 Example5
Batch weight, Kg 14 10 10 10 14
NDC & MEG, Molar Ratio 1:1.75 1:2 1:2 1:2 1:1.75
Manganese acetate, g 6.4 3.7 3.7 3.7 2.6
Mn(OAc)4, ppm as Mn 100 40+40 40+40 40+40 20+20
Sb203,g 4.2 2.4 2.4 2.4 4.0
Sb, ppm as Sb 250 200 200 200 240
Cobalt Acetate, g 1.5 - - - 1.2
Co(OAc)2, ppm as Co 25 - - - 20
RT/BT (Red and Blue Toners), g - 0.02 0.02 0.02 0.02
RT/BT, ppm as such - 2.5 2.5 2.5 1.5
TEPA, g 10.1 5.07 5.07 5.07 15.2
TEPA, ppm as P 100 70 70 70 150
Butylstannoic acid, g - - - - 3.7
Sn, ppm as Sn - - - - 150
- Sodium acetate, g 1.05
Sodium acetate, ppm as such 75
Nanoclay, g 42 - - - -
Nanoclay, ppm as such 3000 - - - -
Nyacol, g - - 28 - -
Nyacol, ppm as such - - 2800 - -
Sodium benzoate, g 4.2 - - 4 -
Sodium benzoate, ppm as such 300 - - 400 -
Aclyn 285, g - - - - 25.2
Aclyn 285, ppm as such - - - - 1800
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Table III- Important characteristics of the amorphous PEN polymer

S.No IV dL/g Carboxyl number meq/kg DEG % L* CIE a* CIE b* CIE Tg«c T^C Tch°C
2 0.527 14 0.64 62.3 -0.7 -1.1 123 267 219
3 0.529 19 0.92 62 -1 -2 122 267 193
4 0.486 20 1.03 65 -2.8 2.9 123 267 203
5 0.523 20 0.74 60.9 -3.3 4 124 269 198
In example 5, addition of manganese acetate and cobalt acetate has reduced the
esterification time to 220 minutes. Similarly addition of Butylstannoic acid and
Antimony trioxide, polymerization catalyst has reduced the polymerization time to 70
minutes.
In example 3, the carboxyl number is 19 and TCh is 193 °C. These two factors are the
main reasons for faster rate of crystallization of PEN chips.
In example 4 and 5, the carboxyl number is 20. The two stage polymerization reaction
has increased the carboxyl number. This increased carboxyl number in turn decreases
the solid state polymerization time.
In example 4 and 5, TCh is 203 and 198 °C respectively. The decreased crystallization
temperature decreases the crystallization time which is evident from table III.
The amorphous PEN resin is heated to 180 °C in an oven and samples are taken at
different time intervals. Crystallinty of these samples are measured in a density gradient
and given in the following table.
Table-IV Rate of Crystallization at 180° C.

S.No Time, min Crystallinity, %t
Eg 2 Eg 3 Eg 4 Eg 5
1. 20 23.85 27.02 28.11 26.85
2. 60 26.12 29.42 30.29 30.25
3. 100 27.22 32.22 33.74 30.01
The rate of crystallization is found to be higher for Example 4. This increase can be due to the addition of nucleating agent Sodium benzoate during the esterification reaction. The percentage crystallinity is comparatively high for example 3 which is attributed to
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the presence of nucleating agent Nyacol. The rate of crystallization is less for Example 2, due to the absence of nucleating agents.
Thus modified PEN (Example 3, 4 and 5) with lower crystallization temperature crystallizes faster than standard PEN (example 2).
The amorphous PEN pellets are charged into an improved Fluid Bed Crystallizer from the top as shown in the Fig. 1. This crystallizer operates with a stream of nitrogen heated to a temperature of 225 °C in 0.1 bar nitrogen pressure for about 40 minutes. The crystallized chips are then subjected to SSP in a batch reactor by heating to 260 °C, initially in the presence of nitrogen, then releasing Nitrogen pressure gradually and maintaining fine vacuum till required I.V. is attained. Since the chips are pre-crystallized for 30 minutes in an improved Fluid Bed Crystallizer it saves about 10 hours of devolatilization process. Moreover this fast crystallizing PEN reduces the SSP time to a greater extend.
Incorporation by Reference
The contents of all cited references (including literature references, patents, patent applications, and websites) that maybe cited throughout this application are hereby expressly incorporated by reference. The practice of the present invention will employ, unless otherwise indicated, conventional techniques of polymer chemistry, which are well known in the art.
Equivalents
The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The foregoing embodiments are therefore to be considered in all respects illustrative rather than limiting of the invention described herein. Scope of the invention is thus indicated by the appended claims rather than by the foregoing description, and all changes that come within the meaning and range of equivalency of the claims are therefore intended to be embraced herein.
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We Claim:
1. A rapidly crystallized amorphous polyethylene naphthalate (PEN) polymer comprising an I.V. of about 0.6 dL/g with a carboxyl end group number of about 18 meq/Kg and a Teh [TCh = crystallization temperature during the 2nd heating cycle] of about 195 °C compared to 220°C for normal PEN.
2. A method of making a polyethylene naphthalate (PEN) polymer as claimed in claim 1, that rapidly crystallizes, the method comprising the following steps:
(a) transesterifying dimethyl 2,6-naphthalene dicarboxylate (NDC) in the
presence
of
(i) monoethylene glycol (MEG);
(ii) at least one transesterification catalyst; and
(iii) at least one nucleating agent, in two stages to form a prepolymer; and
(b) polymerizing the prepolymer at about 250 °C to about 305 °C in the presence
of a polymerization catalyst and at least one thermal stabilizer.
3. A method of making a polyethylene naphthalate (PEN) polymer in which 80% of the
transesterifying step is carried out at about 1050 mbar followed by about 20% of the
transesterifying step being carried out at about 500 mbar, to form the prepolymer.
4. The method according to claim 2 or 3, wherein the transesterifying step is
carried out by progressively increasing the temperature from about 140°C to about 255
°C for about 180 minutes to about 300 minutes.
5. The method according to claim 4, wherein about 80% of the transesterifying step is
carried out at atmospheric pressure.
19

6. The method according to claim 4, wherein about 20% of transesterifying step is carried out by decreasing the pressure to about 500 mbar.
7. The method according to claim 2, wherein about 80% of the transesterifying step is carried out at about 1050 mbar followed by about 20% of the transesterifying step being carried out at about 500 mbar at a temperature of about 230°C to about 255°C.
8. The method according to claim 2, wherein the transesterifying step is carried out for about 180 minutes to about 300 minutes.
9. The method according to claim 2, wherein the transesterification catalyst is an element comprising an element selected from the group consisting of manganese, calcium, zinc, cobalt, antimony, titanium, tin, and a combination thereof.
10. The method according to claim 2, wherein the transesterification catalyst is a compound selected from the group consisting of manganese acetate, titanium acetate, calcium acetate, zinc acetate, antimony trioxide, antimony triacetate, cobalt acetate, tin oxide, and a combination thereof.
11. The method according to claim 9, wherein the manganese acetate is added at about 30 ppm to about 200 ppm as Mn, preferably at about 35 ppm to about 150 ppm as Mn.
12. The method according to claim 2, wherein the transesterification catalyst is added at the start of the transesterifying step.
13. The method according to claim 2, wherein transesterification catalyst is added at the start of the transesterifying step and in the middle of the transesterifying step.
20

14. The method according to claim 2, wherein methanol is removed during the transesterifying step.
15. The method according to claim 2, wherein the molar ratio of NDC:MEG is about
1:1.5 to about 1:2.5.
16. The method according to claim 2, wherein the molar ratio of NDC:MEG is about 1:1.5 to about 1:2.1.
17. The method according to claim 2, wherein the nucleating agent is selected from a group consisting of a sodium compound, a sorbitol, and a nano particle containing compound.
18. The method according to claim 2, wherein the nucleating agent is selected from a group consisting of sodium acetate, sodium benzoate, nano clay, nano particles, micronized sorbitol, sodium salicylate, nyacol, sodium sorbitrate, nano silica, tungsten trioxide, 3,5-di-t-butyl-4-hydroxyphenyl propionic acid methyl ester, ethylene acrylic acid sodium ionomer, and a combination thereof.
19. The method according to claim 19, wherein sodium acetate is added at about 2 ppm to about 200 ppm, preferably about 10 ppm to about 150 ppm.
20. The method according to claim 19, wherein sodium benzoate is added at about 100 ppm to about 1000 ppm, preferably sodium benzoate is added at about 200 ppm to about 800 ppm.
21. The method according to claim 17, wherein nano clay is added at about 100 ppm
to about 3000 ppm, prefeaWy about 1000 ppm to about 4000 ppm, still preferably at about 2500 ppm to about 3000 ppm.
21

22. The method according to claim 2, wherein the nucleating agent is added in the range of about 10 ppm to about 4000 ppm, preferably in the range of about 20 ppm to about 3500 ppm.
23. The method according to claim 2, wherein the transesterifying step further comprises the addition of a color agent.
24. The method according to claim 22, wherein the color agent is a cobalt compound.
25. The method according to claim 30, wherein the color agent is selected from the group consisting of cobalt acetate, 8,9,10,1 l-Tetrachloro-12H-phthaloperin-12-one (Red Toner), l,4-Bis(mesitylamino)anthraquinone (Blue Toner), and a combination thereof.
26. The method according to claim 23, wherein the cobalt compound is added as Co at about 10 ppm to about 80 ppm, preferably, at about 20 ppm to about 60 ppm.
27. The method according to claim 2, wherein the polymerizing step is carried out at about 240 °C to about 285°C, preferably 280 to 285 degrees celsius in the initial stage of the step and about 285 °C to about 305 °C and preferably at about 300 °C to about 305 °C in the later stage of the step at about 2 mbar to complete vacuum.
28. The method according to claim 25, wherein the initial stage is about 40 minutes to about 70 minutes.
29. The method according to claim 35, wherein the final stage is about 15 minutes to about 30 minutes.
22

30. The method according to claim 2, wherein the polymerizing step is carried out by gradually increasing the temperature from about 250 °C to about 305 °C and decreasing the pressure from about 500 mbar to about 2 mbar.
31. The method according to claim 2, wherein the polymerizing cycle is carried out for about 55 minutes to about 100 minutes, preferably for about 100 minutes.
32. The method according to claim 2, wherein the polymerization catalyst is at least one element comprising an element selected from the group consisting of antimony, titanium, germanium, tin, and a combination thereof.
33. The method according to claim 2, wherein the polymerization catalyst is selected from the group consisting of antimony trioxide, tetra-n-butyl titanate (TnBT), butylstannoic acid, and a combination thereof.
34. The method according to claim 2, wherein the polymerization catalyst is antimony trioxide.
35. The method according to claim 2, wherein antimony trioxide is added at about 150 ppm to about 300 ppm as antimony, preferably at about 180 ppm to about 250 ppm.
36. The method according to claim 2, wherein the thermal stabilizer is selected from the group consisting of Triethylphophonoacetate (TEPA), orthophosphoric acid (OPA), and a combination thereof.
37. The method according to claim 2, further comprising the step of adding Ethylene Acrylic Acid Sodium Ionomer product as a nucleating agent after polymerization.
38. The method according to claim 2, wherein a thermal stabilizer is added after the transesterifying step.
23

39. The method according to claim 2, wherein a thermal stabilizer is added at about 40 ppm to about 200 ppm, preferably at about 60 ppm to about 150 ppm.
40. The method according to claim 2, further comprising the step of extruding the PEN melt into strands in water and then cutting them into chips.
41. The method according to claim 37, further comprising the step of crystallizing the chips in a fluid bed crystallizer at about 190 °C to about 230 °C to form precrystallized chips.
42. The method according to claim 37, further comprising the step of crystallizing the chips in a fluid bed crystallizer at about 220 °C to about 230°C to form precrystallized chips.
43. The method according to claim 39, wherein the fluid bed crystallizer is a top entry crystallizer.
44. The method according to claim 37, further comprising the step of subjecting the precrystallized chips to solid state polymerization (SSP) at about 240 °C to about 260 °C initially in the presence of nitrogen, say for 4 hours, then releasing Nitrogen pressure gradually and maintaining fine vacuum till required I.V. is attained
45. An amorphous polyethylene naphthalate (PEN) polymer made by the method of claim 2.
Dated this 19th day of February, 2007.
MOrt\N^WAN
OF R. KfDEWAN & COMPANY
APPLICANTS' PATENT ATTORNEY
24

ABSTRACT
The invention relates to modified Polyethylene Naphthalate (PEN) polymers with fast crystallizing properties, which helps in crystallization of amorphous PEN resin prior to its solid state polymerization (SSP).

Documents:

316-MUM-2007-ABSTRACT(1-7-2009).pdf

316-mum-2007-abstract(complete)-(19-2-2007).pdf

316-mum-2007-abstract(granted)-(7-3-2011).pdf

316-mum-2007-abstract.doc

316-mum-2007-abstract.pdf

316-mum-2007-cancelled pages(3-2-2011).pdf

316-MUM-2007-CLAIMS(1-7-2009).pdf

316-mum-2007-claims(19-2-2007).pdf

316-MUM-2007-CLAIMS(AMENDED)-(17-1-2011).pdf

316-mum-2007-claims(complete)(19-2-2007).pdf

316-mum-2007-claims(granted)-(7-3-2011).pdf

316-MUM-2007-CLAIMS(MARKED COPY)-(17-1-2011).pdf

316-mum-2007-claims.doc

316-mum-2007-claims.pdf

316-mum-2007-correspondance-received.pdf

316-MUM-2007-CORRESPONDENCE(1-7-2009).pdf

316-MUM-2007-CORRESPONDENCE(21-12-2010).pdf

316-MUM-2007-CORRESPONDENCE(29-12-2009).pdf

316-MUM-2007-CORRESPONDENCE(3-2-2011).pdf

316-mum-2007-correspondence(ipo)-(7-3-2011).pdf

316-mum-2007-description (complete).pdf

316-MUM-2007-DESCRIPTION(COMPLETE)-(1-7-2009).pdf

316-mum-2007-description(complete)-(19-2-2007).pdf

316-mum-2007-description(granted)-(7-3-2011).pdf

316-MUM-2007-DRAWING(19-2-2007).pdf

316-mum-2007-drawing(complete)-(19-2-2007).pdf

316-mum-2007-drawing(granted)-(7-3-2011).pdf

316-mum-2007-drawings.pdf

316-MUM-2007-FORM 1(1-7-2009).pdf

316-mum-2007-form 1(19-2-2007).pdf

316-MUM-2007-FORM 1(3-2-2011).pdf

316-mum-2007-form 13(3-2-2011).pdf

316-mum-2007-form 18(2-7-2007).pdf

316-mum-2007-form 2(1-7-2009).pdf

316-mum-2007-form 2(complete)-(19-2-2007).pdf

316-mum-2007-form 2(granted)-(7-3-2011).pdf

316-MUM-2007-FORM 2(TITLE PAGE)-(1-7-2009).pdf

316-MUM-2007-FORM 2(TITLE PAGE)-(3-2-2011).pdf

316-mum-2007-form 2(title page)-(complete)-(19-2-2007).pdf

316-mum-2007-form 2(title page)-(granted)-(7-3-2011).pdf

316-mum-2007-form 2(title page)-(marked copy)-(3-2-2011).pdf

316-MUM-2007-FORM 3(1-7-2009).pdf

316-mum-2007-form 3(16-5-2007).pdf

316-mum-2007-form 3(19-2-2007).pdf

316-mum-2007-form-1.pdf

316-mum-2007-form-2.doc

316-mum-2007-form-2.pdf

316-mum-2007-form-26.pdf

316-mum-2007-form-3.pdf

316-MUM-2007-POWER OF ATTORNEY(17-1-2011).pdf

316-mum-2007-reply to examination report(1-7-2009).pdf

316-mum-2007-reply to examination report(17-1-20011).pdf

316-mum-2007-specification(amended)(1-7-2009).pdf

abstract1.jpg


Patent Number 246603
Indian Patent Application Number 316/MUM/2007
PG Journal Number 10/2011
Publication Date 11-Mar-2011
Grant Date 07-Mar-2011
Date of Filing 19-Feb-2007
Name of Patentee FUTURA POLYESTERS LIMITED
Applicant Address PARAGON CONDOMINIUM,3RD FLOOR, PANDURANG BUDHKAR MARG, MUMBAI-400013,
Inventors:
# Inventor's Name Inventor's Address
1 KULKARNI SANJAY TAMMAJI No.1,Kamarajar Salai,Manali, Chennai 600068
2 BALASUNDARAM DILLYRAJ No.1,Kamarajar Salai,Manali, Chennai 600068
PCT International Classification Number C08G63/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 N/A 1900-01-01 IB