Thermal crystallization of a molten polyester polymer in a fluid

• US 7,192,545 B2
• Filed: 11/10/2004
• Issued: 03/20/2007
• Est. Priority Date: 10/10/2003
• Status: Expired due to Term

• Current Assignee: Alpek Polyester SA de CV
• Original Assignee: Eastman Chemical Company
• Inventors: Ekart, Michael Paul, Jernigan, Mary Therese, Windes, Larry Cates, Wells, Cory Lee
• Primary Examiner(s): Nutter; Nathan M.
• Application Number:
  US10/986,129
• Publication Number:
  US 20050154183A1
• Time in Patent Office: 860 Days
• Field of Search: 528/499, 528/503, 264/176.1, 264/211.13, 264/219
• US Class Current: 264/211.13
• CPC Class Codes: B01J 8/006 by filtration
• CPC Class Codes: B01J 8/007 by sedimentation
• CPC Class Codes: B01J 8/22 gas being introduced into the liquid
• CPC Class Codes: B01J 8/228 externally, i.e. the particles leaving the vessel and subsequently re-entering it
• CPC Class Codes: B29B 13/021 Heat treatment of powders
• CPC Class Codes: B29B 13/065 of powder or pellets
• CPC Class Codes: B29B 2009/165 Crystallizing granules
• CPC Class Codes: B29B 7/42 with screw or helix
• CPC Class Codes: B29B 7/48 with intermeshing devices, e.g. screws
• CPC Class Codes: B29B 7/826 Apparatus therefor
• CPC Class Codes: B29B 7/86 for working at sub- or superatmospheric pressure B01F33/70 takes precedence
• CPC Class Codes: B29B 9/065 under-water, e.g. underwater pelletizers
• CPC Class Codes: B29B 9/16 Auxiliary treatment of granules
• CPC Class Codes: B29C 2793/009 after shaping
• CPC Class Codes: B29C 2949/0715 the preform having one end closed
• CPC Class Codes: B29C 48/022 characterised by the choice of material
• CPC Class Codes: B29C 48/05 Filamentary, e.g. strands
• CPC Class Codes: B29C 48/08 flexible, e.g. films
• CPC Class Codes: B29C 48/285 Feeding the extrusion material to the extruder
• CPC Class Codes: B29C 48/287 Raw material pre-treatment while feeding B29C48/78 takes precedence
• CPC Class Codes: B29C 48/29 : in liquid form
• CPC Class Codes: B29C 49/04 : Extrusion blow-moulding
• CPC Class Codes: B29C 49/06 : Injection blow-moulding
• CPC Class Codes: B29C 51/00 : Shaping by thermoforming , i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor blow moulding of tubular preforms B29C49/00, deforming of tubular or hollow preforms B29C67/0014
• CPC Class Codes: B29K 2067/00 : Use of polyesters or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2105/256 : Sheets, plates, blanks or films
• CPC Class Codes: B29K 2995/004 : Semi-crystalline
• CPC Class Codes: B29L 2031/7158 : Bottles
• CPC Class Codes: C08G 63/88 : Post-polymerisation treatment
• CPC Class Codes: C08J 2367/02 : Polyesters derived from dicarboxylic acids and dihydroxy compounds; C08J2367/06 takes precedence
• CPC Class Codes: C08J 3/12 : Powdering or granulating
• CPC Class Codes: F26B 21/14 : using gases or vapours other than air or steam , e.g. inert gases

Abstract

A process for crystallizing a polyester polymer by introducing a molten polyester polymer, such as a polyethylene terephthalate polymer, into a liquid medium at a liquid medium temperature greater than the T_g of the polyester polymer, such as at a temperature ranging from 100° C. to 190° C., and allowing the molten polyester polymer to reside in the liquid medium for a time sufficient to crystallize the polymer under a pressure equal to or greater than the vapor pressure of the liquid medium. A process flow, underwater cutting process, crystallization in a pipe, and a separator are also described.

Claims

1. A process for crystallizing a polyester polymer comprising introducing a molten polyester polymer, made in the melt phase polycondensation process, into a liquid medium at a liquid medium temperature greater than the T_g of the polyester polymer before the molten polyester polymer falls to a temperature below its T_g.

2. The process of claim 1, wherein the liquid medium temperature is above 100°

C.

3. The process of claim 2, wherein the liquid medium temperature is above 130°

C.

4. The process of claim 3, wherein the liquid medium temperature ranges from 140°

C. to 180°

C.

5. The process of claim 1, wherein the polyester polymer contains at least 60 mole % ethylene units based on the moles of all diols added and at least 60 mole % terephthalate units or naphthalate units based on the moles of all dicarboxylic acids added, and the It.V., of the molten polymer is at least 0.55 dL/g when measured at 25°

C. in a 60/40 wt/wt phenol/tetrachloroethane solvent at a polymer concentration of 0.50 g/100 ml.

6. The process of claim 1, wherein the polyester polymer comprises a polyalkylene terephthalate homopolymer or copolymer modified with 40% or less of repeat units other than alkylene terephthalate.

7. The process of claim 1, wherein the molten polyester polymer is made in a melt phase polycondensation process and introduced into the liquid medium from the melt phase before the molten polyester polymer falls to a temperature below its T_g, and the It.V., of the molten polymer is at least 0.55 dL/g when measured at 25°

C. in a 60/40 wt/wt phenol/tetrachloroethane solvent at a polymer concentration of 0.50 g/100 ml.

8. The process of claim 1, wherein the molten polyester polymer is obtained by heating a solid polyester pellet to above 190°

C. followed by bringing the resulting molten polyester polymer into contact with the liquid medium before the temperature of the molten polyester polymer falls below the T_g of the polymer.

9. The process of claim 1, wherein the molten polyester polymer is extruded in an extruder through a die at a temperature of 190°

C. or more as measured at the extruder nozzle.

10. The process of claim 1, wherein the molten polyester polymer is directed through a die, followed by cutting the molten polyester polymer as it exits the die.

11. The process of claim 1, wherein the molten polyester polymer is cut underfluid in the liquid medium, and the It.V., of the molten polymer is at least 0.55 when measured at 25°

C. in a 60/40 wt/wt phenol/tetrachloroethane solvent at a polymer concentration of 0.50 g/100 ml.

12. The process of claim 11, wherein the molten polyester polymer is cut underfluid into globules.

13. The process of claim 1, wherein the liquid medium temperature when the molten polyester polymer first makes contact with the liquid medium is above the T_g of the polyester polymer, and the It.V. of the molten polymer is at least 0.70 dL/g when measured at 25°

C. in a 60/40 wt/wt phenol/tetrachloroethane solvent at a polymer concentration of 0.50 g/100 ml.

14. The process of claim 1, wherein the molten polyester polymer first makes contact with a liquid medium at a temperature below the T_g of the polyester polymer, and before the temperature of the molten polyester polymer falls below the T_g of the polyester polymer, the liquid medium temperature is above the T_g of the polyester polymer.

15. The process of claim 1, wherein the molten polyester polymer is cut underfluid when the temperature of the polyester polymer is at least 190°

C.

16. The process of claim 1, comprising directing the molten polyester polymer having an It.V., when measured at 25°

C. in a 60/40 wt/wt phenol/tetrachloroethane solvent at a polymer concentration of 0.50 g/100 ml, of at least 0.55 dL/g through a die plate and cutting the molten polyester polymer exiting the die with a cutter located in a liquid medium zone such that the cutter blades and a surface of the die plate are in contact with the liquid medium.

17. The process of claim 1, further comprising a liquid medium zone comprising a die plate and a cutter disposed in a housing containing an inlet and an outlet, and a flow of liquid medium into the housing through the inlet, wherein molten polyester polymer having an It.V., of at least 0.55 dL/g when measured at 25°

C. in a 60/40 wt/wt phenol/tetrachloroethane solvent at a polymer concentration of 0.50 g/100 ml is directed through the die plate, cut with cutter blades on the cutter to form globules, and directed to the outlet of the housing as globules by the motive force of the liquid medium flow.

18. The process of claim 17, wherein the temperature of the liquid medium at the inlet of the housing is less than the temperature of the liquid medium beyond the outlet of the housing.

19. The process of claim 17, wherein the temperature of the liquid medium at the inlet and the outlet of the housing is above the T_g of the polyester polymer.

20. The process of claim 17, wherein the molten polyester polymer is cut underfluid.

21. The process of claim 1, comprising directing molten polyester polymer through a die plate and cutting the molten polyester polymer underfluid as it exits the die with a cutter, wherein the cutter and an inner surface of the die plate are contained in a housing fed with a flow of hot liquid medium at a liquid medium temperature above the T_g of the polyester polymer, and the liquid medium is essentially water.

22. The process of claim 21, wherein the temperature of the liquid medium ranges from 140°

C. to 180°

C.

23. The process of claim 1, comprising allowing the molten polyester polymer to reside in the liquid medium at a liquid medium temperature above the T_g of the polyester polymer for a time sufficient to impart to the molten polyester polymer a degree of crystallinity of at least 15%.

24. The process of claim 23, wherein the degree of crystallinity is above 25%.

25. The process of claim 1, wherein the liquid medium comprises water.

26. The process of claim 1, wherein the liquid medium comprises a polyalkylene glycol.

27. The process of claim 1, wherein the temperature of the liquid medium contacting the molten polyester is greater than the boiling point of the liquid medium at 1 atmosphere.

28. The process of claim 1, comprising crystallizing the molten polyester polymer in the liquid medium at a pressure on the liquid medium which is equal to or higher than the vapor pressure of the liquid medium.

29. The process of claim 1, comprising a pressure on the liquid medium of greater than 25 psia.

30. The process of claim 29, comprising a pressure of 52 psia to 145 psia.

31. The process of claim 1, wherein the liquid medium has a flow to submerge globules obtained from the molten polyester polymer.

32. The process of claim 1, wherein the residence time of the molten polyester polymer or globules made from the molten polyester polymer in said liquid medium to obtain a degree of crystallinity of 20% or more is 10 minutes or less.

33. The process of claim 32, wherein the degree of crystallinity is 30% or more at a residence time of 4 minutes or less.

34. The process of claim 32, wherein the degree of crystallinity is 40% or more.

35. The process of claim of claim 32, wherein the liquid medium temperature ranges from 140°

C. to 180°

C., and the residence time to obtain a degree of crystallinity of 25% or more ranges from greater than 0 seconds to about 8 minutes or less.

36. The process of claim 1, wherein crystallization is conducted in the absence of rotating mechanically induced agitation.

37. The process of claim 1, comprising introducing a feed of liquid, colder than the liquid medium temperature, to the liquid medium containing crystallized polyester polymer or resulting pellets.

38. The process of claim 1, comprising crystallizing the molten polyester polymer in the liquid medium, followed by separating the liquid medium from the crystallized molten polyester polymer while the liquid medium temperature is above the T_g of the polyester polymer.

39. The process of claim 38, comprising directing a cool flow of liquid onto the crystallized molten polyester polymer or resulting pellets after separation from the liquid medium, said cool flow of liquid having a temperature less than the temperature of the crystallized molten polyester polymer or resulting pellets.

40. The process of claim 1, comprising crystallizing the molten polyester polymer under a pressure equal to or greater than the vapor pressure of the liquid medium, followed by depressurizing the resulting crystallized molten polyester polymer or pellets, followed by separating said polymer or pellets from the liquid medium.

41. The process of claim 1, comprising crystallizing the molten polyester polymer under a pressure equal to or greater than the vapor pressure of the liquid medium, followed by separating said polymer or pellets from the liquid medium without substantially decreasing the pressure on the liquid medium immediately prior to separation.

42. The process of claim 1, comprising separating the liquid medium from the resulting crystallized molten polyester polymer or pellets while the pressure on the liquid medium prior to separation is greater than 1 atmosphere.

43. The process of claim 1, wherein the It.V. of the polyester polymer is 0.70 dL/g or greater when measured at 25°

C. in a 60/40 wt/wt phenol/tetrachloroethane solvent at a polymer concentration of 0.50 g/100 ml, the liquid medium comprises water, the molten polyester polymer is cut underwater, and the crystallized polyester polymer is separated from the water under a pressure equal to or greater than the vapor pressure of water.

44. The process of claim 1, wherein crystallized molten polyester polymer or pellets are separated from the liquid medium under a pressure at or above the vapor pressure of the liquid medium with a rotary valve or dual knife-gate valves.

77. The process of claim 1, wherein the molten polyester polymer has an It.V. of at least 0.70 dL/g when measured at 25°

C. in a 60/40 wt/wt phenol/tetrachloroethane solvent at a polymer concentration of 0.50 g/100 ml.

78. The process of claim 77, wherein the molten polyester polymer has an It.V. of at least 0.75 dL/g when measured at 25°

C. in a 60/40 wt/wt phenol/tetrachloroethane solvent at a polymer concentration of 0.50 g/100 ml.

45. A process for separating a crystallized polyester polymer having an It.V., when measured at 25°

C. in a 60/40 wt/wt phenol/tetrachloroethane solvent at a polymer concentration of 0.50 g/100 ml, of at least 0.55 dL/g from a liquid medium comprising introducing molten polyester polymer from a melt phase polycondensation process into hot liquid medium having a temperature greater than the T_g of the polymer before the molten polyester polymer falls to a temperature below its T_g, thereafter forming a crystallized polyester polymer in the hot liquid medium, separating the crystallized polymer from the hot liquid medium under a pressure equal to or greater than the vapor pressure of the liquid medium, and directing a flow of cool liquid onto the crystallized polymer before separation, wherein the temperature of the cool liquid is less than the temperature of the hot liquid medium.

46. The process of claim 45, wherein the temperature of the hot liquid medium is at least 130°

C., and the polyester polymer comprises a polyethylene terephthalate polymer or copolymer.

47. The process of claim 45, wherein the crystallized polyester polymer has a flow in a direction toward a separator, and the cool liquid medium travels countercurrent to the direction of the flow of crystallized polyester polymer.

48. The process of claim 45, wherein the hot liquid medium is separated from globules of crystallized polyester polymer, thereafter leaving a residual hot liquid medium within the interstices of the globules, and the cool liquid is directed onto the globules containing residual hot liquid medium to displace at least a portion of the residual hot liquid medium from the interstices of the globules before separation.

49. The process of claim 45, wherein the hot liquid medium is separated from globules of crystallized polyester polymer, thereafter leaving a residual hot liquid medium within the interstices of the globules traveling in a direction toward a separator, and the cool liquid directed onto the globules containing residual hot liquid medium has a flow rate which is effective to separate a greater amount of the hot liquid medium relative to the amount of hot liquid medium separated in the absence of a flow of cool liquid.

79. The process of claim 45, wherein the molten polyester polymer has an It.V. of at least 0.70 dL/g when measured at 25°

C. in a 60/40 wt/wt phenol/tetrachloroethane solvent at a polymer concentration of 0.50 g/100 ml.

80. The process of claim 79, wherein the molten polyester polymer has an It.V. of at least 0.75 dL/g when measured at 25°

C. in a 60/40 wt/wt phenol/tetrachloroethane solvent at a polymer concentration of 0.50 g/100 ml.

50. A process for crystallizing a molten polyester polymer comprising:

a) directing molten polyester polymer from a melt phase polycondensation process through a die, and

b) before the temperature of the molten polyester polymer falls below its T_g, first contacting the molten polyester with a liquid medium when the liquid medium temperature is greater than the T_g of the polyester polymer and crystallizing the molten polyester polymer.

51. The process of claim 50, wherein the temperature of the molten polyester polymer on contact exceeds the temperature of the liquid medium.

52. The process of claim 51, wherein said molten polyester polymer is a polyethylene terephalate or naphthalate homopolymer or copolymer and having an It.V. of at least 0.55 when measured at 25°

C. in a 60/40 wt/wt phenol/tetrachloroethane solvent at a polymer concentration of 0.50 g/100 ml.

53. The process of claim 52, wherein the temperature of the liquid medium temperature is at least 130°

C.

81. The process of claim 50, wherein the molten polyester polymer has an It.V. of at least 0.70 dL/g when measured at 25°

C. in a 60/40 wt/wt phenol/tetrachloroethane solvent at a polymer concentration of 0.50 g/100 ml.

82. The process of claim 81, wherein the molten polyester polymer has an It.V. of at least 0.75 dL/g when measured at 25°

C. in a 60/40 wt/wt phenol/tetrachloroethane solvent at a polymer concentration of 0.50 g/100 ml.

54. A process for crystallizing a polyester polymer, comprising:

a) directing a molten polyester polymer from a melt phase polycondensation process through a die, and

b) before the temperature of the molten polyester polymer falls below its T_g, contacting the molten polyester with a liquid medium at a liquid medium temperature greater than the T_g of the polyester polymer for a time sufficient to provide a crystallized polyester polymer having a degree of crystallinity of at least 10%, followed by

c) separating, under a pressure equal to or greater than the vapor pressure of the liquid medium, the crystallized polyester polymer from the liquid medium.

55. The process of claim 54, wherein said molten polyester polymer is a polyethylene terephalate or naphthalate homopolymer or copolymer and having an It.V. of at least 0.55 dL/g when measured at 25°

C. in a 60/40 wt/wt phenol/tetrachloroethane solvent at a polymer concentration of 0.50 g/100 ml.

56. The process of claim 55, wherein the temperature of the liquid medium temperature is at least 130°

C.

57. The process of claim 54, wherein the separated crystallized polyester polymer is fed to a dryer to remove residual moisture from the polymer.

58. The process of claim 54, comprising directing a stream of cold liquid onto the molten polyester polymer prior to separation, wherein the temperature of the cold liquid is less than the temperature of the liquid medium.

59. The process of claim 54, comprising drying the separated crystallized polyester polymer, and directing a stream of cold liquid onto the crystallized polyester polymer after separation and before drying, wherein the temperature of the cold liquid is less than the temperature of the separated crystallized polyester polymer.

60. A process for crystallizing a polyester polymer, comprising

a) directing a molten polyester polymer from a melt phase polycondensation process through a die, and

b) before the temperature of the molten polyester polymer falls below its T_g,

i) cutting the polymer into globules with a cutter;

ii) contacting the globules with a flow of liquid medium at a liquid medium temperature greater than the T_g of the polyester polymer to form a flow of slurry;

iii) directing the flow of slurry away from the cutter to a crystallizer and allowing the globules to reside in the crystallization zone under a pressure equal to or greater than the vapor pressure of the liquid medium for a time sufficient to impart a degree of crystallinity of at least 10% to the globules, thereby forming crystallized globules; and

c) separating in a separation apparatus under a pressure equal to or greater than the vapor pressure of the liquid medium, the crystallized globules or resulting pellets from the liquid medium to form a stream of crystallized polyester polymer and a stream of separated liquid medium, wherein;

i) at least a portion of the source of the flow of liquid medium in step bii) is the stream of separated liquid medium; and

ii) the stream of crystallized polyester polymer is directed to a dyer for removing at least a portion of the residual liquid on or in the crystallized polymer.

61. The process of claim 60, wherein the die has an inner surface facing the liquid medium, the molten polymer is cut with cutting blades as the polymer exits the orifices, and the cutting blades and at least a portion of the inner surface of the die plate are in contact with a liquid medium.

62. The process of claim 60, wherein the liquid medium comprises water.

63. The process of claim 60, wherein the flow of liquid medium has a liquid velocity ranging form 1 ft/s to 8 ft/s.

64. The process of claim 60, wherein the crystallizer comprises a pipe having an aspect ration of at least 15:

1.

65. The process of claim 60, wherein the liquid medium temperature in the crystallizer ranges from 100°

C. to 160°

C.

66. The process of claim 60, wherein the pressure on the slurry within the crystallizer ranges from greater than 14.9 psia to 300 psia.

67. The process of claim 60, wherein the crystallizer comprises a pipe ranging from 120 to 9600 ft in length, at a diameter ranging from 4 to 8 inches.

68. The process of claim 67, wherein the slurry flows through the said pipe for 30 seconds to 15 minutes.

69. The process of claim 60, wherein liquid medium level in the separator is to at least the level of globule accumulation within the separator.

70. The process of claim 60, wherein the pressure in the separator is substantially the same as the pressure in the crystallizer.

71. The process of claim 60, wherein a portion of the liquid medium is vented or drained from the separator, cooled to below the liquid medium temperature in the separator, and then fed to the flow of liquid medium in step bii).

72. The process of claim 60, wherein at least a portion of the residual liquid from the dryer is re-circulated to the flow of liquid medium in step bii).

73. The process of claim 60, comprising contacting a stream of cold liquid with globules in the separator, said cold liquid having temperature which is less than the liquid medium temperature in the separator.

74. The process of claim 73, comprising re-circulating at least a portion of the residual liquid removed in the dryer to the source of cold liquid.

75. The process of claim 60, comprising contacting a stream of cold liquid with the stream of crystallized polymer after separation and before entering the dryer, the cold liquid having a temperature which is less than the crystallized polymer temperature.

76. The process of claim 75, comprising re-circulating at least a portion of the residual liquid removed in the dryer to the source of cold liquid.