US20060047102A1 - Spheroidal polyester polymer particles - Google Patents
Spheroidal polyester polymer particles Download PDFInfo
- Publication number
- US20060047102A1 US20060047102A1 US11/018,357 US1835704A US2006047102A1 US 20060047102 A1 US20060047102 A1 US 20060047102A1 US 1835704 A US1835704 A US 1835704A US 2006047102 A1 US2006047102 A1 US 2006047102A1
- Authority
- US
- United States
- Prior art keywords
- spheroids
- residues
- bulk
- mole
- polyester polymer
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 166
- 229920000728 polyester Polymers 0.000 title claims abstract description 131
- 239000002245 particle Substances 0.000 title claims abstract description 80
- 238000002844 melting Methods 0.000 claims abstract description 110
- 230000008018 melting Effects 0.000 claims abstract description 110
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000010438 heat treatment Methods 0.000 claims abstract description 40
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 39
- 150000001875 compounds Chemical group 0.000 claims abstract description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 36
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000008188 pellet Substances 0.000 claims description 149
- 238000000034 method Methods 0.000 claims description 63
- 238000001035 drying Methods 0.000 claims description 35
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 30
- 238000012360 testing method Methods 0.000 claims description 29
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- 230000008025 crystallization Effects 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 26
- 238000010128 melt processing Methods 0.000 claims description 19
- 238000012545 processing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 6
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- 239000007789 gas Substances 0.000 description 54
- 239000000463 material Substances 0.000 description 25
- 230000008569 process Effects 0.000 description 25
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 239000003570 air Substances 0.000 description 19
- 239000000155 melt Substances 0.000 description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- -1 alkylene terephthalate Chemical compound 0.000 description 11
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 230000001965 increasing effect Effects 0.000 description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 description 10
- 239000005020 polyethylene terephthalate Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000002516 radical scavenger Substances 0.000 description 9
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- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 8
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- 238000001938 differential scanning calorimetry curve Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
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- 239000004952 Polyamide Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
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- 238000006068 polycondensation reaction Methods 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
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- 238000005265 energy consumption Methods 0.000 description 2
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- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 239000012925 reference material Substances 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- FQXGHZNSUOHCLO-UHFFFAOYSA-N 2,2,4,4-tetramethyl-1,3-cyclobutanediol Chemical compound CC1(C)C(O)C(C)(C)C1O FQXGHZNSUOHCLO-UHFFFAOYSA-N 0.000 description 1
- IWEATXLWFWACOA-UHFFFAOYSA-N 2,6-dimethylnaphthalene-1-carboxylic acid Chemical compound OC(=O)C1=C(C)C=CC2=CC(C)=CC=C21 IWEATXLWFWACOA-UHFFFAOYSA-N 0.000 description 1
- PXBFMLJZNCDSMP-UHFFFAOYSA-N 2-Aminobenzamide Chemical class NC(=O)C1=CC=CC=C1N PXBFMLJZNCDSMP-UHFFFAOYSA-N 0.000 description 1
- YQPCHPBGAALCRT-UHFFFAOYSA-N 2-[1-(carboxymethyl)cyclohexyl]acetic acid Chemical compound OC(=O)CC1(CC(O)=O)CCCCC1 YQPCHPBGAALCRT-UHFFFAOYSA-N 0.000 description 1
- ICPXIRMAMWRMAD-UHFFFAOYSA-N 2-[3-[2-[3-(2-hydroxyethoxy)phenyl]propan-2-yl]phenoxy]ethanol Chemical compound C=1C=CC(OCCO)=CC=1C(C)(C)C1=CC=CC(OCCO)=C1 ICPXIRMAMWRMAD-UHFFFAOYSA-N 0.000 description 1
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 description 1
- CPHURRLSZSRQFS-UHFFFAOYSA-N 3-[4-[2-[4-(3-hydroxypropoxy)phenyl]propan-2-yl]phenoxy]propan-1-ol Chemical compound C=1C=C(OCCCO)C=CC=1C(C)(C)C1=CC=C(OCCCO)C=C1 CPHURRLSZSRQFS-UHFFFAOYSA-N 0.000 description 1
- CDBAMNGURPMUTG-UHFFFAOYSA-N 4-[2-(4-hydroxycyclohexyl)propan-2-yl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1C(C)(C)C1CCC(O)CC1 CDBAMNGURPMUTG-UHFFFAOYSA-N 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
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- HKVBBCCDZPKANJ-UHFFFAOYSA-N butane-1,4-diol;pentane-1,5-diol Chemical compound OCCCCO.OCCCCCO HKVBBCCDZPKANJ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
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- 150000002466 imines Chemical class 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
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Images
Classifications
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- 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
- C08G63/88—Post-polymerisation treatment
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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- 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
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- 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
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- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29B9/12—Making granules characterised by structure or composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B17/00—Machines or apparatus for drying materials in loose, plastic, or fluidised form, e.g. granules, staple fibres, with progressive movement
- F26B17/12—Machines or apparatus for drying materials in loose, plastic, or fluidised form, e.g. granules, staple fibres, with progressive movement with movement performed solely by gravity, i.e. the material moving through a substantially vertical drying enclosure, e.g. shaft
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B29B9/00—Making granules
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- B29B2009/165—Crystallizing granules
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B2200/00—Drying processes and machines for solid materials characterised by the specific requirements of the drying good
- F26B2200/08—Granular materials
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- 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
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
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- 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
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1355—Elemental metal containing [e.g., substrate, foil, film, coating, etc.]
Definitions
- the field of the invention pertains to polyester polymer particles having a particular morphology and geometry.
- polyester polymer particles and pellets are typically cylindrically shaped, are solid state polymerized, and have high degrees of crystallinity.
- conventional pellets do not usually agglomerate in the dryers which feed an injection molding machine or an extruder. While some sticking occurs at drying temperatures (150° C. to 185° C.), the problem does not usually result in sufficient agglomeration to completely block a flow of pellets from the dryer.
- polyester polymer particle which has a unique morphology and which avoids the need for solid state polymerization.
- This morphology includes one or more of the following features: low melt point, low degree of crystallinity, and high It.V. produced without solid state polymerization.
- these particles if made in a conventional shape, may in some cases stick sufficiently in the dryer that mechanical agitation is required to dislodge them.
- cylindrical solid stated pellets were free flowing in dryer hoppers, while in some cases cylindrical non-solid stated pellets with the unique morphology agglomerated in the pellet dryers.
- T cmax 50% ⁇ CA ⁇ OH
- CA is the total mole % of all carboxylic acid residues other than terephthalic acid residues, based on 100 mole % of carboxylic acid residues in the polyester polymer
- OH is the total mole % of hydroxyl functional compound residues other than ethylene glycol residues, based on 100 mole % of the hydroxyl functional compounds residues; or both B) and C); and optionally but preferably
- polyester polymer spheroids introduced into the drying zone are not solid state polymerized and optionally have one or more of the characteristics described above.
- the spheroids in this embodiment also preferably are within the range of crystallinity mentioned above.
- bottle preforms and stretch blow molded bottles made from the spheroids mentioned above or made by any one of the process embodiments mentioned above.
- FIG. 1 illustrates the geometry and dimensions in inches of the dryer hopper used in the experiments.
- FIG. 2 illustrates the gate test apparatus for the testing the angle of repose of granular materials.
- FIG. 3 illustrates the heap test apparatus for the testing the angle of repose of granular materials.
- FIG. 4 shows a comparison of the angles of repose for the five materials studied by the gate test method.
- FIG. 5 shows a comparison of the angles of repose for the materials studied by the heap test method.
- thermoplastic preform a thermoplastic preform
- article a thermoplastic preform
- container a thermoplastic preform
- container a thermoplastic preform
- container a thermoplastic preform
- container a thermoplastic preform
- container a polymer at a stated temperature or with a heating element
- Reference to processing a polymer at a stated temperature or with a heating element includes other temperatures and additional heating elements, if desired, in addition to the one stated at different times throughout the processing history unless otherwise stated.
- References to a composition containing “an” ingredient or “a” polymer is intended to include other ingredients or other polymers, respectively, in addition to the one named.
- Ranges may be expressed herein as “within” or “between” or from one value to another. In each case, the end points are included in the range. Ranges expressed as being greater than or less than a value exclude the end point(s).
- a temperature means the temperature applied to the polymer unless otherwise expressed as the “actual” polymer or melt temperature.
- ⁇ inh Inherent viscosity at 25° C. at a polymer concentration of 0.50 g/100 mL of 60% phenol and 40% 1,1,2,2-tetrachloroethane
- a bulk of spheroidal polyester polymer pellets having:
- T cmax 50% ⁇ CA ⁇ OH
- CA is the total mole % of all carboxylic acid residues other than terephthalic acid residues, based on 100 mole % of carboxylic acid residues in the polyester polymer
- OH is the total mole % of hydroxyl functional compound residues other than ethylene glycol residues, based on 100 mole % of the hydroxyl functional compounds residues
- the polyester polymer composition is in its isolated form since a degree of crystallinity is imparted, as opposed to polyester compositions in a melt phase process or as a melt in the extruder since as a melt, crystallinity disappears.
- the polyester polymer particles are in the shape of spheroids.
- a spheroid is a particle which is spherical or nearly spherical or globular in shape. It is substantially but imperfectly spherical and can be distinguished from slabs, cylinders, pastilles, cones, rods, or irregular shaped particles having corners.
- Spheroids have a combination of characteristics. For example, spheroids will not stand on either end of the long axis through their center, and they preferably but not necessarily have a y/x ratio of less than 2, where y is the long axis and x is the short axis.
- spheroids will roll from the plate such that no more than 0.5 g of pellets remain on the plate when the plate first makes an angle of 13 degrees with respect to the horizontal.
- the spheroids may be spherical, elliptical, oval, and may have tails to them.
- the spheroids have a peak mode in a roundness distribution less than 1.4, or less than 1.3, or less than 1.2.
- the roundness of a spheroid is defined as perimeter 2 /(4 ⁇ area). “Perimeter” and “area” are defined in the context of a cross-sectional view of a spheroid.
- the spheroid particles can be made by underwater cutting molten polymer flowing through a die into a water housing and cut by blades as the molten stream is forced through the die holes.
- the spheroids are typically not perfectly spherical and usually have a slight tail where they are cut and swept away from the die plate in current of water or other suitable liquid.
- the spheroids desirably have a number average weight of at least 0.10 g per 100 spheroids, more preferably greater than 1.0 g per 100 spheroids, and up to about 100 g per 100 spheroids.
- the volume of the spheroids is not particularly limited, but in one embodiment, there is provided a bulk of spheroids occupying a volume of at least 1 cubic meter, or at least 3 cubic meters, or at least 5 cubic meters.
- the “bulk” of polyester polymer spheroids is at least 10 isolated spheroids, preferably within the weight and volume ranges expressed above.
- the bulk of polyester spheroids exhibit the characteristics expressed herein as an average across a random sampling of 10 or more spheroids in the bulk of spheroids.
- anomalous spheroids which exhibit characteristics either inside or outside of those stated herein.
- the spheroids of the invention exhibit the stated characteristics across a bulk, and these characteristics can be measured by taking a random sampling of at least ten spheroids and determining the stated characteristics as an average across the ten spheroids. All ten spheroids may be measured together in one analysis, or each spheroid may be separately analyzed.
- polyester polymer spheroids is desirably packaged into a container.
- suitable containers to hold the spheroids are storage silos to hold the spheroids while they await shipment from one location to another.
- Another example of a container is a dryer hopper attached to an extruder or injection molding machine.
- Another example of a container to hold the spheroids is a shipping container, such as a Gaylord box, a crate, a railcar, a trailer that can be attached to a truck, a drum, a cargo hold on a ship, or any other suitable package used to transport spheroids.
- containers with spheroids which are finished and ready for shipment or in shipment to a customer for converting the pellets to an article.
- the spheroids have been subjected by the particle manufacturer to all the processing conditions needed to produce a particle with characteristics acceptable to its customers who convert the pellets to articles.
- the converter of pellets places the bulk of the pellets into the dryer hopper and removes residual moisture from the pellets to prevent excessive IV degradation during melt processing.
- the spheroids in the containers have at a minimum the following characteristics:
- T cmax 50% ⁇ CA ⁇ OH
- CA is the total mole % of all carboxylic acid residues other than terephthalic acid residues, based on 100 mole % of carboxylic acid residues in the polyester polymer
- OH is the total mole % of hydroxyl functional compound residues other than ethylene glycol residues, based on 100 mole % of the hydroxyl functional compounds residues; or both B) and C), and preferably
- the bulk of spheroids are not solid state polymerized, and in a more preferred embodiment, there is provided a bulk of spheroids in a container, most preferably a shipping container, which have not been solid state polymerized.
- the polyester polymer spheroids are solid at 25° C. and 1 atmosphere.
- the polyester spheroids have sufficient melt strength to make them suitable for container applications such as bottles and trays.
- the It.V. of the polyester spheroids is at least 0.72 dL/g.
- the It.V. of the polyester spheroids can be at least 0.75 dL/g, or at least 0.78 dL/g, or at least 0.81 dL/g, and up to about 1.2 dL/g, or 1.1 dL/g.
- the polyester polymer spheroids described above have an It.V. of at least 0.75 dL/g.
- polyester polymer of the invention desirably contains alkylene terephthalate or alkylene naphthalate repeat units in the polymer chain. More preferred are polyester polymers which comprise:
- a carboxylic acid component comprising at least 80 mole % of the residues of terephthalic acid, derivates of terephthalic acid, naphthalene-2,6-dicarboxylic acid, derivatives of naphthalene-2,6-dicarboxylic acid, or mixtures thereof, and
- polyesters such as polyethylene terephthalate are made by reacting a diol such as ethylene glycol with a dicarboxylic acid as the free acid or its C 1 - C 4 dialkyl ester to produce an ester monomer and/or oligomers, which are then polycondensed to produce the polyester. More than one compound containing carboxylic acid group(s) or derivative(s) thereof can be reacted during the process. All the compounds that enter the process containing carboxylic acid group(s) or derivative(s) thereof that become part of said polyester product comprise the “carboxylic acid component.” The mole % of all the compounds containing carboxylic acid group(s) or derivative(s) thereof that are in the product add up to 100.
- the “residues” of compound(s) containing carboxylic acid group(s) or derivative(s) thereof that are in the said polyester product refers to the portion of said compound(s) which remains in the said polyester product after said compound(s) is condensed with a compound(s) containing hydroxyl group(s) and further polycondensed to form polyester polymer chains of varying length.
- More than one compound containing hydroxyl group(s) or derivatives thereof can become part of the polyester polymer product(s). All the compounds that enter the process containing hydroxyl group(s) or derivatives thereof that become part of said polyester product(s) comprise the hydroxyl component. The mole % of all the compounds containing hydroxyl group(s) or derivatives thereof that become part of said product(s) add up to 100. The residues of hydroxyl functional compound(s) or derivatives thereof that become part of said polyester product refers to the portion of said compound(s) which remains in said polyester product after said compound(s) is condensed with a compound(s) containing carboxylic acid group(s) or derivative(s) thereof and further polycondensed to form polyester polymer chains of varying length.
- the mole % of the hydroxyl residues and carboxylic acid residues in the product(s) can be determined by proton NMR.
- the polyester polymer comprises:
- a carboxylic acid component comprising at least 90 mole %, or at least 92 mole %, or at least 96 mole % of the residues of terephthalic acid, derivates of terephthalic acid, naphthalene-2,6-dicarboxylic acid, derivatives of naphthalene-2,6-dicarboxylic acid, or mixtures thereof, and
- a hydroxyl component comprising at least 90 mole %, or at least 92 mole %, or at least 96 mole % of the residues of ethylene glycol
- the reaction of the carboxylic acid component with the hydroxyl component during the preparation of the polyester polymer is not restricted to the stated mole percentages since one may utilize a large excess of the hydroxyl component if desired, e.g. on the order of up to 200 mole % relative to the 100 mole % of carboxylic acid component used.
- the polyester polymer made by the reaction will, however, contain the stated amounts of aromatic dicarboxylic acid residues and ethylene glycol residues.
- Derivates of terephthalic acid and naphthalene dicarboxylic acid include C 1 -C 4 dialkylterephthalates and C 1 -C 4 dialkylnaphthalates, such as dimethylterephthalate and 2,6-dimethylnaphthalate.
- the carboxylic acid component(s) of the present polyester may include one or more additional modifier carboxylic acid compounds.
- additional modifier carboxylic acid compounds include mono-carboxylic acid compounds, dicarboxylic acid compounds, and compounds with a higher number of carboxylic acid groups.
- Examples include aromatic dicarboxylic acids preferably having 8 to 14 carbon atoms, aliphatic dicarboxylic acids preferably having 4 to 12 carbon atoms, or cycloaliphatic dicarboxylic acids preferably having 8 to 12 carbon atoms.
- modifier dicarboxylic acids useful as an acid component(s) are phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4′-dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and the like, with isophthalic acid, naphthalene-2,6-dicarboxylic acid, and cyclohexanedicarboxylic acid being most preferable.
- the hydroxyl component of the present polyester may include additional modifier mono-ols, diols, or compounds with a higher number of hydroxyl groups.
- modifier hydroxyl compounds include cycloaliphatic diols preferably having 6 to 20 carbon atoms and/or aliphatic diols preferably having 3 to 20 carbon atoms.
- diols include diethylene glycol; triethylene glycol; 1,4-cyclohexanedimethanol; propane- 1,3-diol; butane-1,4-diol; pentane-1,5-diol; hexane-1,6-diol; 3-methylpentanediol-(2,4); 2-methylpentanediol-(1,4); 2,2,4-trimethylpentane-diol-(1,3); 2,5-ethylhexanediol-(1,3); 2,2-diethyl propane-diol-(1,3); hexanediol-(1,3); 1,4-di-(hydroxyethoxy)-benzene; 2,2-bis-(4-hydroxycyclohexyl)-propane; 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane; 2,2-bis-(3-hydroxyethoxyphen
- the polyester polymer may preferably contain such comonomers as isophthalic acid, naphthalene dicarboxylic acid, cyclohexanedimethanol, and diethylene glycol.
- the polyester pellet compositions may include blends of polyalkylene terephthalates and/or polyalkylene naphthalates along with other thermoplastic polymers such as polycarbonate (PC) and polyamides. It is preferred that the polyester composition should comprise a majority of the polyester polymers, more preferably in an amount of at least 80 wt. %, or at least 95 wt. %, and most preferably 100 wt. %, based on the weight of all thermoplastic polymers (excluding fillers, inorganic compounds or spheroids, fibers, impact modifiers, or other polymers which may form a discontinuous phase). It is also preferred that the polyester polymers do not contain any fillers, fibers, or impact modifiers or other polymers which form a discontinuous phase.
- polyester compositions can be prepared by polymerization procedures known in the art sufficient to effect esterification and polycondensation.
- Polyester melt phase manufacturing processes include direct condensation of a dicarboxylic acid with the diol, optionally in the presence of esterification catalysts, in the esterification zone, followed by polycondensation in the prepolymer and finishing zones in the presence of a polycondensation catalyst; or ester exchange usually in the presence of a transesterification catalyst in the ester exchange zone, followed by prepolymerization and finishing in the presence of a polycondensation catalyst.
- the method for solidifying the polyester polymer from the melt phase process is not limited.
- molten polyester polymer from the melt phase may be directed through a die, or merely cut, or both directed through a die followed by cutting the molten polymer.
- a gear pump may be used as the motive force to drive the molten polyester polymer through the die.
- the molten polyester polymer may be fed into a single or twin screw extruder and extruded through a die, optionally at a temperature of 190° C. or more at the extruder nozzle.
- the polyester polymer is cut at the die head underliquid.
- the polyester polymer melt is optionally filtered to remove particulates over a designated size before being cut. Any other conventional technique known to make spheroids can be used.
- the polyester polymer of the invention is partially crystallized to produce semi-crystalline spheroids.
- the method and apparatus used to crystallize the polyester polymer is not limited, and includes thermal crystallization in a gas or liquid.
- the crystallization may occur in a mechanically agitated vessel; a fluidized bed; a bed agitated by fluid movement; an un-agitated vessel or pipe; crystallized in a liquid medium above the T g of the polyester polymer, preferably at 140° C. to 190° C.; or any other means known in the art.
- the polymer may also be fed to a crystallizer at a polymer temperature below its T g (from the glass), or it may be fed to a crystallizer at a polymer temperature above its T g .
- molten polymer from the melt phase polymerization reactor may be fed through a die plate and cut underwater, and then immediately fed to an underwater thermal crystallization reactor where the polymer is crystallized underwater.
- the molten polymer may be cut, allowed to cool to below its T g , and then fed to an underwater thermal crystallization apparatus or any other suitable crystallization apparatus.
- the molten polymer may be cut in any conventional manner, allowed to cool to below its T g , optionally stored, and then crystallized.
- the crystallized polyester spheroids may be solid stated according to known methods.
- the polyester polymer particles have at least two melting peaks on a DSC first heating scan, wherein one of said at least two melting peaks is a low peak melting point with a peak temperature within a range of 140° C. to 220° C. and having a melting endotherm area of at least the absolute value of 1 J/g.
- melting point is meant the peak temperature of endotherms on a differential scanning calorimeter (DSC) which increases the temperature upward at a rate of 20° C./min on a sample weighing about 10 mg. It is not necessary to run a DSC analysis on the particles, but only that the particles have the stated morphology. The stated tests reveal the properties of the polymer and need only be run to determine whether or not a polymer has or does not have the stated characteristics.
- the low peak melting point is considered to be T m1a as explained further below, which is classified as a melting peak when the area under the heating curve on a DSC first heating scan is at least the absolute value of 1 J/g. If the area under the curve is less than 1 J/g, the uncertainty around whether a curve is truly a peak or not becomes too high. Moreover, one can determine that at least two peaks exist when the endotherm(s) on a DSC scan exhibit at least four slopes, a first slope departing from a baseline, a second slope of opposite sign from the first slope, and a third slope of opposite sign from the second slope, and a fourth slope of opposite sign from the third slope. The temperature location of the peaks on each curve define the melting points on that heating curve. For the purposes of computing the area of the melting endotherms, the dividing point between two peaks is at the point between the peaks where the curve most closely approaches the baseline.
- the first peak is the low peak melting point T m1a
- the second peak is the high peak melting point T m1b such that T m1a ⁇ T m1b .
- the low peak melting point of the polymer particles is within a range of 130° C. to 220° C.
- the low peak melting point of the polyester polymer has a peak temperature of at least 140° C., or at least 150° C., or at least 160° C., or at least 170° C., and does not exceed 210° C., or 200° C., or 195° C.
- the DSC heating curve obtained upon a DSC first heating scan may exhibit an endothermic shoulder on the low-temperature side of the principal endothermic melting peak rather than two separate and well defined melting peaks.
- a low-temperature endothermic shoulder of this type is defined by means of the curve obtained by taking the first derivative with respect to temperature of the original DSC curve. The shoulder appears as a peak in the derivative curve.
- the derivative curve departs the baseline (at temperature A) in the endothermic direction at a temperature preferably less than or equal to 200° C., or less than or equal to 190° C., or less than or equal to 180° C., then achieves a maximum displacement from the baseline, and then reverses direction and approaches or returns to the baseline but does not cross the baseline.
- the derivative curve reverses direction (at temperature B) and again bends towards the endothermic direction, marking the beginning of the primary melting peak in the original DSC curve.
- the heat of melting represented by the shoulder corresponds to the area under the original DSC curve between temperatures A and B, and must be greater than or equal to the absolute value of 1 J/g to be considered a true shoulder.
- minor instrumental noise in the original DSC curve can appear as high-amplitude short-duration spikes in the derivative curve. Such noise can be filtered out by requiring that all features in the derivative curve spanning less than 5° C. be ignored.
- pellets which provide the flexibility of lowering the peak set-point temperature to the heating elements. Either course of action, or both combined, will lower the amount of acetaldehyde generated in the melt processing zone, and also will decrease the cooling time required for a molded article.
- the polymer particles may have one or more melting points which, when measured on a DSC first heating scan, have a heating curve departing from a baseline in the endothermic direction at a temperature of less than or equal to 200° C., or less than or equal to 190° C., or less than or equal to 180° C.
- the DSC heating curve may exhibit only one melting point, or it may exhibit two melting points.
- the heat history of the particles is such that they exhibit at least one melting point which, when measured on a DSC first heating scan, displays a heating curve which begins to depart from the baseline at a temperature of less than or equal to 200° C.
- the area of the endotherm curve represented by the melting peak departing from the baseline below or equal to 200° C. is at least the absolute value of 1 J/g.
- the area of the endotherm curve may be at least the absolute value 1.5 J/g, or at least the absolute value 2 J/g.
- the degree of crystallinity in the polyester composition is less than that found in conventional commercial pellets which normally exceed 55%, and even more than 60%.
- a polymer containing solely terephthalic acid and ethylene glycol residues can attain a maximum degree of crystallinity of 50%.
- a polyester polymer modified with a starting material other than terephthalic acid or ethylene glycol will have a degree of crystallinity less than 50%.
- a polyethylene terephthalate polymer modified with 2 mole % isophthalic acid residues and 2.7 mole % diethylene glycol residues will have a maximum degree of crystallinity of 45.3% (50-2-2.7).
- the pellets are crystallized to a degree of crystallization of at least 25%, or at least 30%, or at least 32%. While there is no preferred upper limit below the maximum degree of crystallinity calculated as set forth in the formula, in many cases the degree of crystallinity does not exceed 45%, or not more than 40%.
- Pellet melting temperature and the degree of crystallinity are determined using Differential Scanning Calorimetry (DSC).
- the sample weight for this measurement is 10 ⁇ 1 mg and the sample consists of either (1) a portion of a single pellet, or more preferably (2) a sample taken from several grams of cryogenically ground pellets.
- the first heating scan is performed. The sample is heated from approximately 25° C. and proceeds upward to about 290° C. at a rate of 20° C./minute.
- the absolute value of the area of the melting endotherms (one or more) minus the area of any crystallization exotherms is determined. This area corresponds to the net heat of melting and is expressed in Joules/gram.
- the heat of melting of 100% crystalline PET is taken to be 119 Joules/gram, so the weight fraction crystallinity of the pellet is calculated as the net heat of melting divided by 119. To obtain the weight. % crystallinity, the weight fraction crystallinity is multiplied by 100. Unless otherwise stated, the melting point in each case is also determined using the same DSC scan.
- the percent crystallinity is calculated from both of:
- the low peak melting point and degree of crystallinity of the polyester polymer are obtained by and influenced by a number of crystallization conditions and other factors. These conditions and factors include controlling the temperature conditions applied to the polymer during crystallization, the residence time within the crystallization zone, the nature of the polymer, the efficiency of the medium used to crystallize the polymer, and the strain undergone by the polymer.
- crystallization conditions include controlling the temperature conditions applied to the polymer during crystallization, the residence time within the crystallization zone, the nature of the polymer, the efficiency of the medium used to crystallize the polymer, and the strain undergone by the polymer.
- Those of skill in crystallizing polyester polymer are aware of the suitable conditions in conventional crystallizers to adjust the melting point and the degree of crystallinity, and can obtain polymers having a melting point and a degree of crystallinity within the stated ranges for a given polymer composition. For example, mild thermal crystallization temperatures of 100° C. to 200° C.
- polyester polymers of varying compositions will attain different melting points from other polyester polymers even at the same degrees of crystallinity. Processing separate samples of compositionally identical polyester polymers at varying residence times under the same temperature conditions will also produce polyester polymers with varying degrees of crystallinity. Accordingly, the degree of crystallization can vary among two polymers of the same composition. Also, the melting point can vary among two polymers of different composition even if their degree of crystallinity is identical.
- the polyester polymer composition is preferably made from at least 75% virgin polyester polymer, more preferably at least 78 wt. %, and can be 89 wt. % or more, or 95 wt. % or more virgin material, or entirely of virgin material.
- Virgin material may include scrap or regrind polymer, but is distinguished from post consumer recycle polymer. However, while virgin material may contain scrap or regrind material, in one embodiment, scrap or reground material is absent from the virgin polymer.
- a virgin polymer with a level of crystallinity and melting point outside of the ranges can be remelted, for example in an extruder, followed by thermal crystallization at relatively mild temperatures (100 to 200° C.).
- melt-phase polymerization to an intermediate molecular weight (It.V.
- the polyester can be crystallized at mild temperatures to a degree of crystallization within the stated range, followed by solid-state polymerizing also at mild temperatures ranging from 170° to 200° C. to increase the It.V. to that suitable for container applications, although in this latter case, the residence time in the solid state polymerization zone is either increased, the pressure further decreased, the inert gas flow rate increased, or any combination thereof.
- the polyester polymer is manufactured in a melt phase polycondensation reaction to an It.V. of at least 0.72 dL/g.
- a shipping container containing polyester spheroids which have not been solid-state polymerized and have the It.V., melting point, and AA characteristics described herein.
- the spheroids are fed into a dryer followed by melt processing the spheroids to form an article, in which the spheroids have not been solid-state polymerized and have the characteristics described above.
- pellets subjected to a solid state polymerization process are typically first crystallized to impart a degree of crystallinity and a melting point sufficiently high to avoid sticking at the high temperature conditions applied in the solid state polymerization zone.
- the crystallization process preceding a solid state polymerization process generally imparts to the pellets high degrees of crystallinity to mitigate agglomeration in the solid state reactors which run at high temperatures.
- the pellets obtained from the solid stating process generally have high melting points of about 220° C. or more.
- the high melting points have the disadvantage of increasing the temperature of the polymer melt in the extruder by a few degrees, thereby increasing the cooling time required for molded products which can increase the cycle time of the machine and increase the potential for more acetaldehyde formation.
- pellets obtained from solid state polymerization processes also tend to have a high degree of crystallinity, in excess of about 50%, which increases the latent heat of fusion, thereby increasing the energy required to melt the spheroids.
- the high temperatures applied to the polymer for long times can at times actually over-anneal the polymer, with the effect that some spheroids do not completely melt in the melt processing zone and thereby cause deformities in the molded or extruded product. Accordingly, it is preferred not to solid state polymerize the spheroids, and to provide spheroids with suitable It.V. made in the melt phase process for the production of the spheroids.
- the polyester spheroids of the invention preferably contain 10 ppm or less acetaldehyde (as measured by ASTM F2013-00 “Determination of Residual Acetaldehyde in Polyethylene Terephthalate Bottle Polymer Using an Automated Static Head-Space Sampling Device and a Capillary GC with a Flame Ionization Detector”), and more desirably, about 7 ppm or less, or 3 ppm or less residual acetaldehyde (“AA”). This may be accomplished by gas stripping the AA from the spheroids.
- an acetaldehyde scavenger may be added to the polymer, which has the attendant advantage of also reducing the acetaldehyde generation rate. If the scavenger is added after the AA stripping is essentially complete, the scavenger will lower the amount of AA in the molded article, such as a bottle perform, by reacting with AA that is formed upon melting. If an excess of scavenger is added prior to the AA stripping or instead of the AA stripping, there may be some that is not consumed and can lower the amount of AA in the molded article. Alternatively, there may be two or more addition points for an M scavenger.
- a gas such as air or an inert gas such as nitrogen is contacted with the polyester polymer spheroids either co-current or countercurrent, preferably countercurrent to the flow of the spheroids in a vessel in a continuous or batchwise process, preferably a continuous process.
- the temperature of the gas introduced into the AA stripping vessel is not particularly limited, but preferably from ambient to 40° C., and more preferably about ambient.
- the temperature of the gas exiting the stripping vessel will approximate the temperature of the pellets introduced into the vessel. Thus, if spheroids are introduced at 100° C., the exit temperature of the gas will be about 100° C.+/ ⁇ 20° C.
- the temperature of the gas exiting the vessel should not exceed the temperature at which the molecular weight of the spheroids is advanced in the solid state.
- the residence time of the spheroids depends on the gas temperature and spheroid mass/gas ratio, but in general, the residence time ranges from 1 hour to 24 hours.
- the gas composition is not particularly limited, and includes nitrogen, carbon dioxide, or ambient air.
- the gas does not need to be dried, since the function of the gas is not to dry the pellets but to strip residual AA from the pellets. If desired, however, the gas may be dried.
- gas stripping of acetaldehyde may also occur in the dryer feeding the extruder for making an article, it is preferred to feed the dryer with polymer spheroids already having 10 ppm or less of residual acetaldehyde in order to reduce the gas flow used in the dryer and/or improve the quality of the articles made from the extruder.
- dry gas is not required to strip the AA from the spheroids, whereas in a drying process, a stream of dried air is circulated through the spheroids primarily to reduce the moisture on or in the spheroids with the secondary advantage of also removing AA.
- ambient air can be and preferably is used as the stripping medium.
- spheroids having an It.V. of at least 0.72 dL/g and either a degree of crystallinity within a range of 20% to Tcmax, or a low peak melting point in the range of 130° C. to 220° C., or both are fed to a vessel, preferably through the upper end of a vessel, as hot spheroids (e.g. 100° C.
- the vessel can be pressurized, it is preferably not pressurized except by the pressure created from the gas flow.
- the vessel is desirably operated at about 0-5 psig, or ambient pressure.
- the gas can be introduced into the vessel by any conventional means, such as by a blower, fans, pumps, and the like.
- the gas may flow co-current to or countercurrent to or across the flow of particles through the vessel.
- the preferred flow of gas through the bed of particles is countercurrent to the particle flow through the bed.
- the gas can be introduced at any desired point on the vessel effective to reduce the level of acetaldehyde in the particles fed to the vessel.
- the gas introduction point is to the lower half of the bed height in the vessel, and more preferably to the lower 1 ⁇ 4 of the bed height.
- the gas flows through at least a portion of the particle bed, preferably through at least 50 volume % of the bed, more preferably through at least 75% of the particle bed volume.
- Any gas is suitable for use in the invention, such as air, carbon dioxide, and nitrogen. Some gases are more preferred than others due to the ready availability and low cost. For example, the use of air rather than nitrogen would lead to significant operating cost improvements. It was believed that the use of nitrogen gas was required in operations which pass a hot flow of gas through a bed of particles at temperatures above 180° C., such as in a crystallizer, because nitrogen is inert to the oxidative reactions which would otherwise occur between many polyester polymers and ambient oxygen resulting in pellet discoloration. However, by keeping the process temperature low such that the gas exiting the vessel does not exceed 190° C., particle discoloration is minimized.
- the gas contains less than 90 vol % nitrogen, or less than 85 vol % nitrogen, or less than 80 vol % nitrogen. In another embodiment, the gas contains oxygen in an amount of 17.5 vol % or more.
- ambient composition the composition of the air at the plant site on which the vessel is located
- air which is not separated or purified is preferred. Desirably, ambient air is fed through the gas inlet. While the air can be dried if desired, it is not necessary to dry the air since the object is to remove acetaldehyde from the particles.
- any vessel for containing particles and allowing a feed of gas and particles into and out of the vessel is suitable.
- a vessel having at least an inlet for gas, and inlet for the polyester polymer particles, an outlet for the gas, and an outlet for the finished particles.
- the vessel is preferably insulated to retain heat.
- the gas inlet and the finished particle outlet are desirably located below the gas outlet and the particle inlet, preferably with the gas outlet and particle inlet being toward the top of the vessel and the gas inlet and finished particle outlet being toward the bottom of the vessel.
- the gas is desirably introduced into the bed within the vessel at about 1 ⁇ 2 or 1 ⁇ 4 of the bed height within the vessel.
- the particles are preferably introduced at the top of the vessel, and move by gravity to the bottom of the vessel, while the gas preferably flows countercurrent to the direction of the particle flow.
- the particles accumulate within the vessel to form a bed of particles, and the particles slowly descend down the length of the vessel by gravity to the finished particle outlet at the bottom of the vessel.
- the bed height is not limited, but is preferably at a substantially constant height in a continuous process and is at least 75% of the height of the vessel containing the particles within the stripping zone.
- the vessel preferably has an aspect ratio L/D of at least 2, or at least 4, or at least 6.
- the process can be conducted in a batch or semi batch mode in which as the particles would not flow and the stream of gas can be passed through the bed of particles in any direction
- the process is preferably continuous in which a stream of particles continuously flows from the particle inlet to the finished particle outlet as the particles are fed to the vessel.
- a suitable gas flow rate introduced into the vessel and passing through at least a portion of the particle bed is one which is sufficient to reduce the amount of residual acetaldehyde on the particles introduced into the vessel.
- suitable gas flow rates introduced into the vessel are at least 0.0001 standard cubic feet per minute (SCFM), or at least 0.001 SCFM, or at least 0.005 SCFM.
- SCFM standard cubic feet per minute
- High flow rates are also suitable, but not necessary, and the gas flow rate should be kept sufficiently low to avoid unnecessary energy consumption by the gas pumps, fans, or blowers.
- the gas flow rate is preferably not any higher than 0.15 SCFM, or not higher than 0.10 SCFM, or not higher than 0.05 SCFM, or even not higher than 0.01 SCFM for every one (1) pound of charged particles per hour.
- an acetaldehyde scavenger may be added to the polyester polymer either near the end of the melt-phase production of the polymer or by melt blending the high IV spheroids with the scavenger. Addition of scavenger to the melt-phase production of polymer should be done as late as possible, preferably near the end of the finisher stage, i.e., near the end of the last stage under vacuum, or more preferably after the finisher stage. Compounding to form polymer concentrates with relatively high loadings of an acetaldehyde scavenger is known in the art. The polyester concentrate contains at least about 0.5 wt. % of the scavenging component in the polyester.
- These concentrates can be added via an extruder, or liquid dispersions of said scavenging component can be added via a pump, near the end of the melt-phase production of the polymer while the polymer is still molten.
- these polymer concentrate particles can be blended with polymer spheroids at temperatures which maintain both types of particles in the solid phase.
- the blend of concentrate and polymer spheroids can then be fed to an extruder, preferably an extruder used to mold plastic articles, such as bottle preforms.
- a melt-phase process to produce polymer particles can employ a combination of acetaldehyde stripping and acetaldehyde scavengers added near the very end or exit of the melt-phase process.
- the particles exiting the stripping zone can be blended with concentrate particles at temperatures which maintain both types of particles in the solid form.
- acetaldehyde scavengers are any of those known in the art, and in particular, amino-terminated polyamides having a molecular weight of less than 25,000 g/mol, or less than 20,000 g/mol, or less than 12,000 g/mol, and preferably the reaction products of adipic acid with m-xylylene diamine.
- the end groups of these polyamides form ‘imines’ with AA and virtually bind it into the polyamide chain ends.
- polyester polymer spheroids may be fed to an extruder suitable to make containers or sheet after being dried to remove moisture from the spheroids. Accordingly, there is also provided a method of melt processing polyester polymer spheroids comprising:
- the drying zone comprises a dryer. Dryers feeding a melt processing zone reduce the moisture content of spheroids. Moisture in or on spheroids fed into a melt extrusion chamber will cause the melt to lose excessive It.V. at melt temperatures by hydrolyzing the ester linkages with a resulting negative impact on the melt flow characteristics of the polymer and stretch ratio of the preforms when blown into bottles. Therefore, prior to extrusion the spheroids are dried with a flow of hot dry gas at a temperature of 140° C. or more to drive off most of the moisture on and in the particle. It is desirable to dry the spheroids at high temperatures of 140° C. or more to decrease the residence time of the spheroids in the dryer and increase throughput. In general, the typical residence time of spheroids in the dryer at conventional temperatures (140° C. to 190° C.) will be on average from 0.75 hours to 12 hours.
- the spheroids may be contacted with a flow of heated air or inert gas such as nitrogen to raise the temperature of the spheroids and remove volatiles from inside the spheroids, and may also be agitated by a rotary mixing blade or paddle.
- the flow rate of the heating gas if used, is a balance between energy consumption, residence time of spheroids, and preferably avoiding the fluidization of the spheroids. Suitable gas flow rates range from 0.05 to 100 SCFM for every pound per hour of spheroids discharged from the dryer, preferably from 0.2 to 5 SCFM per lb/hr of spheroids.
- the spheroids of the invention exhibit a lower tendency to agglomerate in the dryer at drying temperatures than conventional geometric shaped particles which have not been polymerized in the solid state or having similar characteristics.
- melt processing zone to form molten polyester polymer, followed by forming an article such as a sheet or a molded part.
- a melt processing zone Any conventional technique used to melt spheroids and form articles therefrom can be used.
- Suitable melt processing zones include extruders equipped with a barrel, one or more screws in the barrel, a motor to turn the screw, heating elements to direct heat through the barrel to the spheroids, and a die plate through which the molten polymer is forced.
- the die may be a sheet die, optionally connected to a thermoforming mold.
- Another melt processing zone is an injection molding machine equipped with the same features, except that a nozzle is used instead of a die through which the polymer is forced into a runner system that directs the polymer into one or more mold cavities.
- a molded part includes a bottle preform (parison).
- composition of the present invention can be added neat to the bulk polyester, may added as a dispersion in a liquid carrier or may be added to the bulk polyester as a polyester concentrate containing at least about 0.5 wt. % of the component in the polyester let down into the bulk polyester.
- suitable components include crystallization aids, impact modifiers, surface lubricants, stabilizers, denesting agents, antioxidants, ultraviolet light absorbing agents, metal deactivators, colorants, nucleating agents, acetaldehyde lowering compounds, reheat rate enhancing aids, sticky bottle additives such as talc, and fillers and the like can be included.
- the resin may also contain small amounts of branching agents such as trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylol propane, pyromellitic dianhydride, pentaerythritol, and other polyester forming polyacids or polyols generally known in the art. All of these additives and many others and their use are well known in the art and do not require extensive discussion. Any of these compounds can be used in the present composition.
- the articles of manufacture are not limited, and include sheet and bottle preforms.
- the bottle preforms can be stretch blow molded into bottles by conventional processes.
- containers be made from spheroids made according to the process of this invention, but other items such as sheet, film, bottles, trays, other packaging, rods, tubes, lids, filaments and fibers, and other molded articles may also be manufactured using the polyester spheroids of the invention.
- Made from polyethylene terephthalate, beverage bottles suitable for holding water or carbonated beverages, and heat set beverage bottles suitable for holding beverages which are hot filled into the bottle are examples of the types of bottles which are made from the crystallized spheroids of the invention.
- Voridian PET CB12 polyester polymer is commercially available from Eastman Chemical Company.
- CB12 pellets are approximately cylindrical in shape and are produced from cutting a strand of polymer.
- CB12 pellets are semi-crystalline and solid-stated.
- UWC and UW AC pellets were produced on an underwater pelletization apparatus using Voridian PET CB12 polyester polymer as a feed. Although the It.V. of these pellets was not measured, CB12 polyester processed in this manner typically has an It.V. of 0.78 to 0.82 dL/g. These pellets are spheroidal by the definition previously set forth.
- UWC pellets were made by cutting resin underwater at a water temperature of about 160° C., thus yielding semi-crystalline pellets.
- the residence time of the pellets in the pressurized hot water crystallizer was about 5 minutes.
- UW AC pellets were made by cutting resin underwater at a water temperature of about 90° C., so the pellets were amorphous. They were subsequently crystallized in the small batch paddle crystallizer. Room temperature pellets were charged into the crystallizer preheated to a set point of 210° C. Average pellet temperature (measured using an IR pyrometer “gun”) was about 157° C. after 30 minutes and about 162° C. after 35 minutes. The pellets were then discharged into buckets and allowed to cool naturally.
- 16-3001 polymer is modified with 3.0 mole % isophthalic acid and about 3.6 mole % diethylene glycol. It was polymerized to a final It.V. of about 0.82 in the melt phase and underwent standard cut-strand pelletization to produce typical approximately cylindrical pellets.
- the pellets were crystallized in a continuous process by passing it through two horizontal jacketed elongated vessels which were agitated by a longitudinal shaft with radially-mounted paddles.
- the heating medium circulated through the jacket was set at 180° C., which yielded a temperature for the pellets exiting the vessel of about 165° C. Residence time of the polymer in the vessels was about 30 minutes.
- 12-3001 polymer is modified with 3.0 mole % isophthalic acid and about 3.6 mole % diethylene glycol. It was polymerized to a final It.V. of about 0.82 in the melt phase and underwent standard cut-strand pelletization to produce typical approximately cylindrical pellets. The pellets were crystallized in a batch rotary double-coned dryer by heating the polymer up to 180° C., then cooling back to ambient.
- Table 1 summarizes key information about the spherical and cylindrical pellets used for this work.
- RPU pellets were made on a Roll Processing Unit using Voridian PET CB12 polyester polymer as a feed. RPU pellets are “slabical” in shape, and all of the pellets used for this work had nominal lateral dimensions of 3 ⁇ 3 mm and thickness of 2.25 to 2.5 mm (0.090 to 0.100 inch). The RPU pellets were made at a rate of about 325 lb/hr with the calendar roll temperature set-point of about 150° C.
- Table 2 summarizes key information about the RPU pellets used for this work. Sheet temperature was measured using an IR pyrometer “gun” and is therefore the temperature of the sheet surface. The It.V. of the RPU 150 and RPU 179 pellets was not measured, but (based on many measurements of other pellets made using similar drying and extrusion conditions) is expected to be in the 0.79 to 0.81 range. Crystallinity was determined, in duplicate, from first-heat DSC run at 20° C./min by summing the heat of fusion (in J/g) of all melting peaks, subtracting the heat of any crystallization peaks, and dividing by 119 (the heat of fusion, in J/g, of 100% crystalline PET).
- the pellets were heated in a hopper of a dryer.
- the dryer consisted of a bank of five hoppers serviced by a single Conair drying unit by means of an insulated manifold system.
- the pellets to be investigated were placed in Hopper 1 (first hopper on the supply manifold), dummy pellets were placed in Hopper 3, and the air supply valves to Hoppers 2, 4, and 5 were closed. This procedure was followed to prevent excessively high air flow through Hopper 1.
- FIG. 1 illustrates the geometry and dimensions in inches of the dryer hopper used in the experiments.
- the base of the hopper is sealed by simple sliding gate valve. The slide may be completely removed to fully open the hopper exit.
- the dryer was thoroughly preheated to its operating temperature prior to charging the hopper with pellets.
- Hopper 3 was charged with about 20 pounds (roughly 80% of the hopper capacity) of dummy pellets (typically CB12) and a similar quantity of test pellets were loaded into Hopper 1.
- a sheathed thermocouple was inserted into the bed of test pellets with its tip several inches below the bed surface and the temperature was periodically recorded.
- the residence time of the pellets in Hopper 1 was a uniform 3.0 hours.
- the slide was removed from the gate valve and, if the pellets did not freely flow from the hopper exit, the base of the hopper at the gate valve was struck sharply by hand with the edge of the slide. This “whacking” was repeated at a deliberate pace until pellet flow commenced, up to a maximum of 20 whacks. If the pellet bed remained stuck after this, a rod was inserted into the open gate valve up through the pellet bed. A single jab of the rod was always sufficient to cause rapid pellet flow and complete emptying of the hopper; multiple strokes or “chipping” were never required.
- the DSC results for the all of RPU pellets fed to the dryer were very similar with the only feature being a single melting peak departing the baseline at 195-200° C. and peaking at 250-252° C.
- the DSC results for the 16-3001 pellets and the UWC AC and UWC pellets showed an obvious feature of a the low melting temperature endotherm departing from the baseline at about 160° C. and centered at 181° C.
- the low melting temperature endotherm peaked at 174° C., indicating a pellet crystallization temperature of 155-160° C.
- the final temperature achieved by the pellets in the hopper was 190° C. At 30 minutes the temperature was 180° C.; at 45 minutes, 187° C.; at 60 minutes, 188° C.; and at 90 minutes and beyond, 190° C. The pellet temperature closely approached equilibrium after about 45 minutes, and truly achieved its ultimate value after about 90 minutes.
- the spheroidal pellets both the UW AC and the UWC pellets—are far less sticky at elevated temperature than either the slabical RPU pellets or the cylindrical 16-3001 pellets.
- spheroidal pellets Crystallized both in air and in water were free flowing, while all of the other types of pellets required at least 5 whacks to induce flow (there is not enough data to say this with certainty for the RPU 150 pellets, but based on the data that does exist it seems a near-certain assumption).
- the 16-3001 pellets were crystallized at a temperature and in a manner very similar to the UW AC pellets, and both types of pellets have very similar composition and IV.
- the angle of repose PET pellets of various shapes and morphologies was analyzed.
- the angle of repose is a measure of the frictional properties of a granular material and may be related to the propensity of pellets to stick in a dryer. A higher angle of repose means that the pellets are more likely to stick in a dryer, whereas a lower angle of repose indicates a material is more free-flowing.
- FIGS. 2 and 3 show fixtures for the testing of angle of repose of granular materials.
- the test fixtures were designed to function inside a large dryer at elevated temperatures.
- the dryer is equipped with a baffle to direct air flow through the test fixtures and heat the pellets effectively.
- the gate test ( FIG. 2 ) is a box comprising a wire mesh base 1 , two fixed side walls 3 , a fixed back wall 5 , and a vertically removable side, or gate 7 .
- the inside dimensions of the gate test box are 5.75 ⁇ 5.75 ⁇ 8.00 inches.
- the gate 7 is held in place with a latch to allow the box to be filled with pellets 9 .
- the dryer is turned on at time zero. After the appropriate elapsed time, the dryer is opened and the pellet temperature is measured with a Raytek Raynger MX IR pyrometer (model# RAYMX4PCFU). The gate 7 is then slowly lowered vertically until the top edge of the gate 7 is lower than the base 1 and the gate 7 is able to be removed.
- the heap test ( FIG. 3 ) is a stationary platform inside a moveable box.
- the box has four welded sides 21 and a wire mesh bottom.
- the inside dimensions of the heap test box are 5.75 ⁇ 5.75 ⁇ 3.00 inches.
- the box was then mounted onto a jack stand 23 with holes drilled in it to allow air flow through the pellets 25 .
- the jack stand comprised legs 31 , a jacking screw 33 , and a height adjustment knob 35 .
- the rod 37 passed through holes in the bottom of the box and the jack stand 23 .
- the box was raised so that the disc 22 was in contact with the bottom of the box.
- the box was then filled with pellets 25 .
- Drying times were between 3 and 8 hours and drying temperature setpoints were between 165 C and 185 C. These conditions were chosen to approximate dryer operation conditions commonly practiced commercially.
- the gate test consistently produced higher measured angles of repose. While the temperature bias may explain part of the difference, a temperature range of 20 C experienced within each test method according to the experimental design produced less variation than observed between test methods with a 10 C temperature bias. Thus, it is reasonable to conclude that the geometry of the test method has a significant influence on the results.
- FIG. 4 shows a comparison of the angles of repose for the five materials studied by the gate test method.
- the five data points for each material represent all of the time/temperature combinations investigated. Over a range of drying times and temperatures, the spheroidal UWC material exhibited a much lower angle of repose than the other cylindrical or slabical materials. From this data, the pellet geometry appears to more important in providing a low angle of repose than the morphology of the material.
- FIG. 5 shows a similar analysis for the heap test.
- the five data points for each material represent all of the time/temperature combinations investigated.
- the spheroidal UWC pellets have a significantly lower angle of repose than any of the other cylindrical or slabical materials. From this data, the pellet geometry appears to more important in providing a low angle of repose than the morphology of the material.
- the spheroidal UWC pellets consistently provide the lowest angle of repose. Given the differences in the results between the gate and the heap tests, it is difficult to detect a meaningful trend in the data as a function of annealing time for the same pellet geometry and very similar compositions (16-3001, 12-3001, and CB12). At the start of the experiment, a hypothesis was that annealing during crystallization and/or solid-stating reduces the amount of amorphous material that may participate in inter-pellet interactions at drying temperatures and thus annealing would lead to decreased angles of repose. While there is some indication of this with the gate test data set, the geometrical effect is much stronger.
- spheroid pellets having an angle of repose of less than 34.0°, or less than 32.0°, or 31.0° or less, or 30.0° or less, in a gate test at an actual pellet temperature of 165° C. after 5 hours.
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Priority Applications (27)
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MYPI20053640 MY150897A (en) | 2004-09-02 | 2005-08-04 | Spheroidal polyester polymer particles |
CN2005800294216A CN101023114B (zh) | 2004-09-02 | 2005-08-29 | 椭球形聚酯聚合物颗粒 |
PT57917528T PT1784439E (pt) | 2004-09-02 | 2005-08-29 | Partículas esferóides de polímero de poliéster |
KR1020107023574A KR101198712B1 (ko) | 2004-09-02 | 2005-08-29 | 회전타원체형 폴리에스터 중합체 입자 |
PL05791752T PL1784439T3 (pl) | 2004-09-02 | 2005-08-29 | Kuliste cząstki polimeru poliestrowego |
CN2010105278138A CN102020763B (zh) | 2004-09-02 | 2005-08-29 | 椭球形聚酯聚合物颗粒 |
BRPI0514775A BRPI0514775B1 (pt) | 2004-09-02 | 2005-08-29 | massa de partículas esferoides de polímero de poliéster, e, método para secar e processar em fusão partículas esferoides de polímero de poliéster |
JP2007530193A JP2008511732A (ja) | 2004-09-02 | 2005-08-29 | スフェロイド形ポリエステルポリマー粒子 |
PCT/US2005/030535 WO2006028749A2 (en) | 2004-09-02 | 2005-08-29 | Spheroidal polyester polymer particles |
CN201210237466.4A CN102746494B (zh) | 2004-09-02 | 2005-08-29 | 椭球形聚酯聚合物颗粒 |
MX2007002405A MX2007002405A (es) | 2004-09-02 | 2005-08-29 | Particulas de polimero de poliester esferoidales. |
KR1020077007104A KR101217340B1 (ko) | 2004-09-02 | 2005-08-29 | 회전타원체형 폴리에스터 중합체 입자 |
EP05791752.8A EP1784439B1 (en) | 2004-09-02 | 2005-08-29 | Spheroidal polyester polymer particles |
ES05791752.8T ES2460740T3 (es) | 2004-09-02 | 2005-08-29 | Partículas de polímeros de poliéster esferoidales |
EP10188434.4A EP2289969B1 (en) | 2004-09-02 | 2005-08-29 | Spheroidal polyester polymer particles |
CA2576919A CA2576919C (en) | 2004-09-02 | 2005-08-29 | Spheroidal polyester polymer particles |
ARP050103655A AR050854A1 (es) | 2004-09-02 | 2005-09-01 | Particulas esferoides de polimero de poliester |
TW094130022A TWI313276B (en) | 2004-09-02 | 2005-09-02 | Spheroidal polyester polymer particles |
US11/454,271 US8022168B2 (en) | 2004-09-02 | 2006-06-16 | Spheroidal polyester polymer particles |
JP2010236896A JP2011012284A (ja) | 2004-09-02 | 2010-10-21 | スフェロイド形ポリエステルポリマー粒子 |
US12/909,099 US20110092663A1 (en) | 2004-09-02 | 2010-10-21 | Spheroidal polyester polymer articles |
JP2012000783A JP2012062493A (ja) | 2004-09-02 | 2012-01-05 | スフェロイド形ポリエステルポリマー粒子 |
ARP120100107A AR084839A2 (es) | 2004-09-02 | 2012-01-12 | Particulas esferoides de polimero de poliester |
JP2013134174A JP5774639B2 (ja) | 2004-09-02 | 2013-06-26 | スフェロイド形ポリエステルポリマー粒子 |
JP2014107027A JP2014145090A (ja) | 2004-09-02 | 2014-05-23 | スフェロイド形ポリエステルポリマー粒子 |
JP2015109983A JP2015147947A (ja) | 2004-09-02 | 2015-05-29 | スフェロイド形ポリエステルポリマー粒子 |
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US61895104P | 2004-10-15 | 2004-10-15 | |
US11/018,357 US20060047102A1 (en) | 2004-09-02 | 2004-12-21 | Spheroidal polyester polymer particles |
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EP (2) | EP2289969B1 (ko) |
JP (6) | JP2008511732A (ko) |
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CN (3) | CN102020763B (ko) |
AR (2) | AR050854A1 (ko) |
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PT (1) | PT1784439E (ko) |
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US20060235188A1 (en) * | 2004-09-02 | 2006-10-19 | Stephen Weinhold | Spheroidal polyester polymer particles |
US20070270533A1 (en) * | 2003-10-10 | 2007-11-22 | Ekart Michael P | Thermal crystallization of a molten polyester polymer in a fluid |
US20080154021A1 (en) * | 2003-09-18 | 2008-06-26 | Eastman Chemical Company | Thermal crystallization of polyester pellets in liquid |
US20090315219A1 (en) * | 2008-06-19 | 2009-12-24 | Eastman Chemical Company | Screw designs having improved performance with low melting pet resins |
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