WO1992002569A1 - Polymer pellet configuration for solid-state polymerization - Google Patents

Polymer pellet configuration for solid-state polymerization Download PDF

Info

Publication number
WO1992002569A1
WO1992002569A1 PCT/US1991/005399 US9105399W WO9202569A1 WO 1992002569 A1 WO1992002569 A1 WO 1992002569A1 US 9105399 W US9105399 W US 9105399W WO 9202569 A1 WO9202569 A1 WO 9202569A1
Authority
WO
WIPO (PCT)
Prior art keywords
solid
polymer
pellet
pellets
state polymerization
Prior art date
Application number
PCT/US1991/005399
Other languages
French (fr)
Inventor
Cheuk Chung Yau
Original Assignee
Eastman Kodak Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Company filed Critical Eastman Kodak Company
Priority to EP91914427A priority Critical patent/EP0541674B1/en
Priority to DE69104206T priority patent/DE69104206T2/en
Publication of WO1992002569A1 publication Critical patent/WO1992002569A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/06—Conditioning or physical treatment of the material to be shaped by drying
    • B29B13/065—Conditioning or physical treatment of the material to be shaped by drying of powder or pellets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/80—Solid-state polycondensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention relates to polymer pellet configuration for solid—state polymerization. More specifically, the present invention relates to pellets having a short path length for volatiles to be removed from the pellets, and a reduced contact area among pellets to minimize sticking of the pellets undergoing solid—state polymerization in a stationary or moving bed reactor.
  • polyethylene terephthalate may be prepared in the molten state by polycondensation accompanied by liberation of ethylene glycol from prepolycondensates in autoclaves of conventional design. Intrinsic viscosities of approximately 0.7 are usually obtained. Intrinsic viscosities as high as 1.00 can be obtained in specifically designed reactors which improve the evaporation of glycol.
  • These prior art processes have the disadvantage that high reaction temperatures, high catalyst concentrations and long reaction time periods are required to achieve high relative viscosities. The inevitable result is an increasing thermal degradation of the melt which manifests itself by a large number of carboxyl end groups and an intensive yellow coloring of the end product.
  • a high percentage of carboxyl end groups leads to strong signs of degradation during the re elting of the polycondensate.
  • the discolorations are particularly undesirable if pellucid polycondensates are needed for the manufacture of, for instance, packing material for foodstuffs or beverages.
  • elevated concentrations of aldehydes are to be expected in the melt. These properties are particularly undesirable if the end product is used to manufacture beverage bottles.
  • the aldehydes diffuse into the liquid and affect the flavor of these beverages. Further, such aldehyde containing beverages may be considered to be unfit for human consumption by certain regulatory bodies.
  • Figure 1 is a plan view of a pellet according to the present invention taken along lines 1—1 of Figure 2;
  • Figure 2 is a side view of the pellet shown in Figure 1;
  • Figure 3 is a modification of the pellet according to the present invention;
  • Figure 4 is a view showing two pellets stacked together. Description of the Invention
  • a polymer pellet having improved reactivity for solid state polymerization and less tendency to stick during processing with heat, the pellet having opposite faces generally lying in parallel planes, and in cross—section in a plane parallel to the faces the pellet having a generally rectangular central section, the corners thereof protruding into generally rounded lobes, the generally rectangular central section having dimensions A and B wherein the ratio of A to B is 1.2 to 6 and the ratio of B to the average radius of said lobes is 0.3 to 5.
  • the polymer of the pellet according to this invention may be any polymer which is to be polymerized in the solid state.
  • Preferred polymers are polyesters, and in particular poly(ethylene terephthalate) or copolymers thereof.
  • polyesters such as poly(ethylene terephthalate) are produced to an intermediate molecular weight of, say 0.4—0.65 in a melt phase, by reacting a dicarboxylic acid or ester with a glycol using suitable catalysts under conventional reaction condition well known in the art. Following melt phase polymerization, the polymer may be subjected to further polymerization in the solid state.
  • Solid state polymerization is a well known technique for building up molecular weight of a polymer in the solid state.
  • One conventional solid—stating operation takes place in so—called plug flow reactors wherein polymer pellets are introduced into the top of a tall cylindrical vessel and removed from the bottom at the same rate. During the residence times in the reactor, which is commonly in the order of 8—18 hours, the pellets reach high temperatures, generally 200—250°C.
  • Molecular weight as measured by inherent viscosity (I.V.), increases during the time the pellets are in the reactor. Typically, I.V. is increased from a range of 0.4—0.65 to greater than 0.7. This process is thoroughly described in U.S. Patent No. 4,064,112, which is incorporated herein by reference.
  • Described herein is a design of the cross section of the pellets that incorporates into a pellet of a given weight a reduced path length the volatiles need to travel to the exterior of the pellet to increase solid—state polymerization rate, and reduced contact area among pellets to minimize sticking.
  • This design will also reduce the initial degradation experienced by the pellets during solid—state polymerization because the shorter path allows the moisture content of the pellets to leave in much shorter times and minimize the probability of hydrolytic degradation.
  • the design is shown in Figures 1 and 2.
  • Figure 1 illustrates pellet 10 having a generally rectangular central section 12 having dimensions A and B.
  • the corners of section 12, 14, 16, 18 and 20 are illustrated in broken lines and protrude into generally rounded lobes 22, 24, 26 and 28, respectively.
  • the lobes are preferably rounded as shown in Figure 1, but may be of the general shape shown in Figure 3 wherein the C dimension would be an average distance or radius as indicated in Figure 3 by broken line 30.
  • the optimal design has the ratio of B to C of 1 and the ratio of A to B ranging from 1.6 to 4, although the benefit of this design can still be realized when the ratio of B to C varies from 0.3 to 5 and the ratio A to B varies from 1.2 to 6.
  • the ratio of B to C is greater than 1, the cross section of the pellet has the general shape as shown in Figure 1.
  • the advantage of the mentioned design can be demonstrated in Figure 4 wherein the pellets 10 and 11 can be stacked with minimum amount of surface contact. The added space between the two pellets also allows carrier gas to pass through to remove volatiles generated during solid-state polymerization thus increasing the rate of solid-state polymerization.
  • the pellets of the present invention can be obtained by conventional methods, such as by extruding the polymer melt through a die with the die holes taking the shape as shown in Figure 1.
  • the extruded polymer can then be chilled to form a solid rod and be cut into pellets of desired lengths.
  • the length (1) of the pellets preferably ranges from 0.05 to 0.2 inch but can vary from 0.03 to 0.3 inch.
  • the dies can have any number of holes normally ranging from 1 to 100.
  • the opposite upper and lower faces 13 and 15 of pellet 10 are theoretically in generally parallel planes. However, under production conditions, these faces may not be perfectly flat or parallel due to the fact that the cutter is cutting a continuously moving strand of polymer and upon cooling of the pellet there may be slight distortion.
  • lobes 22, 24, 26 and 28 are generally rounded. However, they do not have to be perfectly round and may even resemble portions of a square or rectangle as shown in Figure 3. In this case, the average diameter, or an arc 30 would be used as the C dimension.
  • the following example is submitted for a better understanding of this invention.
  • Pellets with cross sections taking the shape of a circle, square, rectangle and design according to this invention are prepared by extruding poly(ethylene) terephthalate with a 0.76 I.V. through a die plate with the corresponding shape of die holes.
  • the circular, square and rectangular shapes are for comparison.
  • the extruded rods are quenched in chilled water and cut into pellets with an average weight of 0.0177 g/pellet using a rotary cutter.
  • the pellets are crystallized at 180°C and the solid—state polymerization rates are measured. The results are shown in Table 1.
  • I.V. inherent viscosity

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

Disclosed is a configuration for a polymer pellet having improved reactivity for solid-state polymerization and less tendency to stick during processing with heat. The pellets have a reduced path length for volatiles to travel to the exterior of the pellet, and reduced contact area in a packed condition.

Description

POLYMER PELLET CONFIGURATION FOR SOLID-STATE POLYMERIZATION
Technical Field The present invention relates to polymer pellet configuration for solid—state polymerization. More specifically, the present invention relates to pellets having a short path length for volatiles to be removed from the pellets, and a reduced contact area among pellets to minimize sticking of the pellets undergoing solid—state polymerization in a stationary or moving bed reactor.
It is known that polyethylene terephthalate may be prepared in the molten state by polycondensation accompanied by liberation of ethylene glycol from prepolycondensates in autoclaves of conventional design. Intrinsic viscosities of approximately 0.7 are usually obtained. Intrinsic viscosities as high as 1.00 can be obtained in specifically designed reactors which improve the evaporation of glycol. These prior art processes have the disadvantage that high reaction temperatures, high catalyst concentrations and long reaction time periods are required to achieve high relative viscosities. The inevitable result is an increasing thermal degradation of the melt which manifests itself by a large number of carboxyl end groups and an intensive yellow coloring of the end product. A high percentage of carboxyl end groups leads to strong signs of degradation during the re elting of the polycondensate. The discolorations are particularly undesirable if pellucid polycondensates are needed for the manufacture of, for instance, packing material for foodstuffs or beverages. In addition, simultaneous with the discoloration, elevated concentrations of aldehydes are to be expected in the melt. These properties are particularly undesirable if the end product is used to manufacture beverage bottles. The aldehydes diffuse into the liquid and affect the flavor of these beverages. Further, such aldehyde containing beverages may be considered to be unfit for human consumption by certain regulatory bodies.
In order to avoid these disadvantages, it is known to produce high viscosity polyesters in the solid phase at temperatures below the melting point of these condensates and under an inert gas blanket or vacuum.
The drawbacks of this improvement are the large efforts and expenditure required to prevent the granulate from sticking in the course of the solid state polycondensation. In one attempted solution to solve this sticking problem, the prior art has subjected the granulate to a continuous mechanically produced movement during the solid state polycondensation. Another prior art attempt to solve this stickiness problem is to effect the solid state polycondensation in a fluidized bed in the presence of hot inert gases, such as nitrogen. In order to avoid agglomerations due to stickiness the prior art has also added the so—called anticaking agents to the surface of the polycondensed granulate.
Brief Description of the Drawings
Figure 1 is a plan view of a pellet according to the present invention taken along lines 1—1 of Figure 2; Figure 2 is a side view of the pellet shown in Figure 1; Figure 3 is a modification of the pellet according to the present invention; and Figure 4 is a view showing two pellets stacked together. Description of the Invention
According to the present invention, there is provided a polymer pellet having improved reactivity for solid state polymerization and less tendency to stick during processing with heat, the pellet having opposite faces generally lying in parallel planes, and in cross—section in a plane parallel to the faces the pellet having a generally rectangular central section, the corners thereof protruding into generally rounded lobes, the generally rectangular central section having dimensions A and B wherein the ratio of A to B is 1.2 to 6 and the ratio of B to the average radius of said lobes is 0.3 to 5.
The polymer of the pellet according to this invention may be any polymer which is to be polymerized in the solid state. Preferred polymers are polyesters, and in particular poly(ethylene terephthalate) or copolymers thereof.
Typically, polyesters such as poly(ethylene terephthalate) are produced to an intermediate molecular weight of, say 0.4—0.65 in a melt phase, by reacting a dicarboxylic acid or ester with a glycol using suitable catalysts under conventional reaction condition well known in the art. Following melt phase polymerization, the polymer may be subjected to further polymerization in the solid state.
Solid state polymerization is a well known technique for building up molecular weight of a polymer in the solid state. One conventional solid—stating operation takes place in so—called plug flow reactors wherein polymer pellets are introduced into the top of a tall cylindrical vessel and removed from the bottom at the same rate. During the residence times in the reactor, which is commonly in the order of 8—18 hours, the pellets reach high temperatures, generally 200—250°C. Molecular weight, as measured by inherent viscosity (I.V.), increases during the time the pellets are in the reactor. Typically, I.V. is increased from a range of 0.4—0.65 to greater than 0.7. This process is thoroughly described in U.S. Patent No. 4,064,112, which is incorporated herein by reference.
Described herein is a design of the cross section of the pellets that incorporates into a pellet of a given weight a reduced path length the volatiles need to travel to the exterior of the pellet to increase solid—state polymerization rate, and reduced contact area among pellets to minimize sticking. This design will also reduce the initial degradation experienced by the pellets during solid—state polymerization because the shorter path allows the moisture content of the pellets to leave in much shorter times and minimize the probability of hydrolytic degradation. The design is shown in Figures 1 and 2.
Figure 1 illustrates pellet 10 having a generally rectangular central section 12 having dimensions A and B. The corners of section 12, 14, 16, 18 and 20 are illustrated in broken lines and protrude into generally rounded lobes 22, 24, 26 and 28, respectively. The lobes are preferably rounded as shown in Figure 1, but may be of the general shape shown in Figure 3 wherein the C dimension would be an average distance or radius as indicated in Figure 3 by broken line 30.
The optimal design has the ratio of B to C of 1 and the ratio of A to B ranging from 1.6 to 4, although the benefit of this design can still be realized when the ratio of B to C varies from 0.3 to 5 and the ratio A to B varies from 1.2 to 6. When the ratio of B to C is greater than 1, the cross section of the pellet has the general shape as shown in Figure 1. The advantage of the mentioned design can be demonstrated in Figure 4 wherein the pellets 10 and 11 can be stacked with minimum amount of surface contact. The added space between the two pellets also allows carrier gas to pass through to remove volatiles generated during solid-state polymerization thus increasing the rate of solid-state polymerization.
The pellets of the present invention can be obtained by conventional methods, such as by extruding the polymer melt through a die with the die holes taking the shape as shown in Figure 1. The extruded polymer can then be chilled to form a solid rod and be cut into pellets of desired lengths. The length (1) of the pellets preferably ranges from 0.05 to 0.2 inch but can vary from 0.03 to 0.3 inch. The dies can have any number of holes normally ranging from 1 to 100. The opposite upper and lower faces 13 and 15 of pellet 10 are theoretically in generally parallel planes. However, under production conditions, these faces may not be perfectly flat or parallel due to the fact that the cutter is cutting a continuously moving strand of polymer and upon cooling of the pellet there may be slight distortion.
The preferred design is for lobes 22, 24, 26 and 28 to be generally rounded. However, they do not have to be perfectly round and may even resemble portions of a square or rectangle as shown in Figure 3. In this case, the average diameter, or an arc 30 would be used as the C dimension. The following example is submitted for a better understanding of this invention.
Pellets with cross sections taking the shape of a circle, square, rectangle and design according to this invention are prepared by extruding poly(ethylene) terephthalate with a 0.76 I.V. through a die plate with the corresponding shape of die holes. The die holes have the following dimensions: circular, 5.09 mm in diameter; square, 4.51 x 4.51 mm; rectangular, 2.61 x 7.82 mm; according to invention, A = 6.39, B = 2.13, C = 1.69 mm (dimensions from Figure 1). The circular, square and rectangular shapes are for comparison. The extruded rods are quenched in chilled water and cut into pellets with an average weight of 0.0177 g/pellet using a rotary cutter. The pellets are crystallized at 180°C and the solid—state polymerization rates are measured. The results are shown in Table 1.
Table 1. Effect of Pellet Shape on Solid—State Polymerization Rate of PET
Solid—State Polymerization Pellet Shape Rate (dL/g-h) round (comparative) 0.01410 square (comparative) 0.01372 rectangle (comparative) 0.01594
Design shown in Figures 1 0.01934 and 2
I.V. (inherent viscosity) is measured at 25°C using 0.50 gram of polymer per 100 mL of a solvent consisting of 60% by weight phenol and 40% by weight tetrachloroethane.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims

1. A polymer pellet having improved reactivity for solid—state polymerization, and less tendency to stick during processing with heat, said pellet characterized by having opposite faces lying generally in parallel planes, and in cross-section in a plane parallel to said faces said pellet having a generally rectangular central section, the corners thereof protruding into lobes, said generally rectangular central section having dimensions A and B wherein the ratio of A to B is 1.2 to 6 and the ratio of B to the average radius of said lobes is 0.3 to 5.
2. A polymer pellet according to Claim l wherein said corners protrude into generally rounded lobes.
3. A polymer pellet according to Claim 1 wherein the ratio of A to B is 1.6 to 4.
4. A polymer pellet according to Claim 1 wherein the ratio of B to C is 0.7 to 3.
5. A polymer pellet according to Claim 1 wherein the length of the pellets is 0.05 to 0.2 inch.
6. A polymer pellet according to Claim 1 wherein the polymer is a polyester.
PCT/US1991/005399 1990-08-03 1991-07-31 Polymer pellet configuration for solid-state polymerization WO1992002569A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP91914427A EP0541674B1 (en) 1990-08-03 1991-07-31 Polymer pellet configuration for solid-state polymerization
DE69104206T DE69104206T2 (en) 1990-08-03 1991-07-31 POLYMERE PELLET CONFIGURATION FOR POLYMERIZATION IN SOLID STATE.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/563,024 US5145742A (en) 1990-08-03 1990-08-03 Polymer pellet configuration for solid-state polymerization
US563,024 1990-08-03

Publications (1)

Publication Number Publication Date
WO1992002569A1 true WO1992002569A1 (en) 1992-02-20

Family

ID=24248787

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/005399 WO1992002569A1 (en) 1990-08-03 1991-07-31 Polymer pellet configuration for solid-state polymerization

Country Status (9)

Country Link
US (1) US5145742A (en)
EP (1) EP0541674B1 (en)
JP (1) JPH06500133A (en)
AT (1) ATE111929T1 (en)
CA (1) CA2079326A1 (en)
DE (1) DE69104206T2 (en)
DK (1) DK0541674T3 (en)
ES (1) ES2060404T3 (en)
WO (1) WO1992002569A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5391694A (en) * 1993-10-15 1995-02-21 Shell Oil Company Solid state polymerization of polyesters with low diffusion resistance prepolymer granules
JPH10195204A (en) * 1997-01-14 1998-07-28 Toray Ind Inc Polyester granular chip
KR20020074245A (en) * 2001-03-19 2002-09-30 주식회사 파웰 High efficiency soft-switching AC-DC boost converter using coupled inductor and energy recovery circuit having power factor correction function
DE102004012579A1 (en) * 2004-03-12 2005-09-29 Bühler AG Process for the preparation of a partially crystalline polycondensate
EP2055458A1 (en) * 2006-08-11 2009-05-06 Mitsui Chemicals, Inc. Pellets comprising polymer and package
US8968615B2 (en) 2004-09-02 2015-03-03 Eastman Chemical Company Low melting polyester polymers

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5393863A (en) * 1993-01-04 1995-02-28 Eastman Chemicali Company Production of branched polyesters
US5393871A (en) * 1993-01-04 1995-02-28 Eastman Chemical Company Production of polyesters and polyester articles having good clarity
DE19505680C1 (en) * 1995-02-20 1996-05-23 Inventa Ag Condensn. injection moulding of preform for food-quality bottle
US6048922A (en) * 1997-08-20 2000-04-11 Eastman Chemical Company Process for preparing high strength fiber reinforced composites
US6043313A (en) 1997-09-04 2000-03-28 Eastman Chemical Company Thermoplastic polyurethane additives for improved polymer matrix composites and methods of making and using therefor
US20030060596A1 (en) * 2001-07-18 2003-03-27 Turner Sam Richard Amorphous copolyesters
US7834127B2 (en) * 2001-07-18 2010-11-16 Eastman Chemical Company Amorphous copolyesters
US20040151854A1 (en) * 2003-02-03 2004-08-05 Pecorini Thomas Joseph Extrusion blow molded articles
ITPD20040038A1 (en) * 2004-02-16 2004-05-16 Plastic Systems Srl DEHUMIDIFICATION PROCESS OF PLASTIC MATERIALS IN GRANULES AND PLANT OPERATING IN ACCORDANCE WITH SUCH PROCESS
DE102004014590A1 (en) * 2004-03-23 2005-10-20 Buehler Ag Semicrystalline polyethylene terephthalate
DE102007055242A1 (en) 2007-11-16 2009-05-20 Bühler AG Process for the crystallization of crystallizable polymers with high tendency to adhere
US7868125B2 (en) * 2008-03-03 2011-01-11 Eastman Chemical Company Production of non-solid-stated polyester particles having solid-stated properties
DE102009009957A1 (en) 2009-02-23 2010-08-26 Bühler AG Process for the production of polyester particles at high throughput in one line
AT508252B1 (en) 2009-12-28 2010-12-15 Erema METHOD AND DEVICE FOR PREPARING PARTIAL CRYSTALLINE POLYMER MATERIAL
EP2671902B1 (en) 2012-06-05 2018-01-03 Polymetrix AG Polyamide conditioning
PL2712881T3 (en) 2012-09-26 2015-10-30 Polymetrix Ag Method and apparatus for directly crystallisation of polymers under inert gas
US10745517B2 (en) 2012-09-26 2020-08-18 Polymetrix Ag Process and apparatus for direct crystallization of polycondensates
KR101564500B1 (en) * 2014-03-12 2015-10-29 주식회사 효성 Method for preparing a polyester resin for high polymerization purpose
EP4257629A3 (en) 2017-02-17 2024-01-10 Polymetrix AG Method and device for direct crystallisation of polycondensates
US20210101313A1 (en) * 2017-04-26 2021-04-08 The Coca-Cola Company Multilobed polyester pellets
EP3650186B1 (en) 2018-11-08 2023-07-19 Polymetrix AG Method and device for direct crystallisation of polycondensates
EP3708936B1 (en) 2019-03-15 2024-04-17 Polymetrix AG Method for recycling of polyolefins

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4064112A (en) * 1975-12-31 1977-12-20 Zimmer Aktiengesellschaft Process for the continuous production of high molecular weight polyethylene terephthalate
EP0284544A2 (en) * 1987-03-26 1988-09-28 Shell Internationale Researchmaatschappij B.V. Solid state polymerization of polyester prepolymers
EP0335819A2 (en) * 1988-04-01 1989-10-04 The Goodyear Tire & Rubber Company Preparation of ultra-high molecular weight polyester
EP0354159A1 (en) * 1988-08-03 1990-02-07 Shell Internationale Researchmaatschappij B.V. Solid state polymerization of porous pills made by compacting polyester prepolymers

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3188264A (en) * 1962-12-21 1965-06-08 Tektronix Inc Loose fill packing material
US3595737A (en) * 1967-09-11 1971-07-27 Anaconda Wire & Cable Co Pellet for improved extrusion method
US4169179A (en) * 1977-10-07 1979-09-25 Bussey Harry Jun Spring-like loose fill packaging material
US4166875A (en) * 1977-10-07 1979-09-04 Bussey Harry Jr Free-flowing packaging material
DE2848338A1 (en) * 1978-11-08 1980-05-22 Hoechst Ag FREE-FLOWING PACKING MATERIAL MADE OF FOAMED PLASTIC

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4064112A (en) * 1975-12-31 1977-12-20 Zimmer Aktiengesellschaft Process for the continuous production of high molecular weight polyethylene terephthalate
US4064112B1 (en) * 1975-12-31 1994-09-13 Davy Mckee Aktiengesellschaft Process for the continuous production of high molecular weight polyethylene terephalate
EP0284544A2 (en) * 1987-03-26 1988-09-28 Shell Internationale Researchmaatschappij B.V. Solid state polymerization of polyester prepolymers
EP0335819A2 (en) * 1988-04-01 1989-10-04 The Goodyear Tire & Rubber Company Preparation of ultra-high molecular weight polyester
EP0354159A1 (en) * 1988-08-03 1990-02-07 Shell Internationale Researchmaatschappij B.V. Solid state polymerization of porous pills made by compacting polyester prepolymers

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5391694A (en) * 1993-10-15 1995-02-21 Shell Oil Company Solid state polymerization of polyesters with low diffusion resistance prepolymer granules
WO1995010557A1 (en) * 1993-10-15 1995-04-20 Shell Internationale Research Maatschappij B.V. Solid state polymerisation of polyesters with low diffusion resistance prepolymer pellets
US5412063A (en) * 1993-10-15 1995-05-02 Shell Oil Company Solid state polymerization of polyesters with low diffusion resistance prepolymer granules
JPH10195204A (en) * 1997-01-14 1998-07-28 Toray Ind Inc Polyester granular chip
KR20020074245A (en) * 2001-03-19 2002-09-30 주식회사 파웰 High efficiency soft-switching AC-DC boost converter using coupled inductor and energy recovery circuit having power factor correction function
DE102004012579A1 (en) * 2004-03-12 2005-09-29 Bühler AG Process for the preparation of a partially crystalline polycondensate
US8968615B2 (en) 2004-09-02 2015-03-03 Eastman Chemical Company Low melting polyester polymers
EP2055458A1 (en) * 2006-08-11 2009-05-06 Mitsui Chemicals, Inc. Pellets comprising polymer and package
EP2055458A4 (en) * 2006-08-11 2013-04-03 Mitsui Chemicals Inc Pellets comprising polymer and package
US8617706B2 (en) 2006-08-11 2013-12-31 Mitsui Chemicals, Inc. Pellets comprising polymer and package containing the same

Also Published As

Publication number Publication date
DE69104206D1 (en) 1994-10-27
EP0541674B1 (en) 1994-09-21
CA2079326A1 (en) 1992-02-04
ATE111929T1 (en) 1994-10-15
JPH06500133A (en) 1994-01-06
DK0541674T3 (en) 1994-10-17
EP0541674A1 (en) 1993-05-19
DE69104206T2 (en) 1995-01-19
ES2060404T3 (en) 1994-11-16
US5145742A (en) 1992-09-08

Similar Documents

Publication Publication Date Title
US5145742A (en) Polymer pellet configuration for solid-state polymerization
US7329723B2 (en) Thermal crystallization of polyester pellets in liquid
US10370486B2 (en) Polyester polymer particles having a small surface to center molecular weight gradient
US5393871A (en) Production of polyesters and polyester articles having good clarity
US5412063A (en) Solid state polymerization of polyesters with low diffusion resistance prepolymer granules
CN1673251A (en) Method for the production of highly condensed polyester granulate
TW200906902A (en) High molecular weight polyester polymers with reduced acetaldehyde
EP0977793B1 (en) Process for the preparation of polyesters
US5830982A (en) Production of poly (ethylene terephthalate)
JP2004143442A (en) Method for producing polyester resin
KR100942881B1 (en) Method for Increasing Solid State Polymerization Rate of Polyester Polymers
US4849497A (en) Solid state polymerization of porous pills made by compacting polyester prepolymers
US4977196A (en) Solid state polymerization of porous pills made by compacting polyester prepolymers
US5393863A (en) Production of branched polyesters
JP2004123917A (en) Method for manufacturing polyester resin
US6124423A (en) Process for crystallizing polyethylene naphthalate copolymers in the absence of devolatilization

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP KR

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU NL SE

WWE Wipo information: entry into national phase

Ref document number: 2079326

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 1991914427

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1991914427

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1991914427

Country of ref document: EP