EP1082377A1 - Verfahren zur herstellung einer thermoplastischen polymervorform sowie ein daraus hergestellter gegenstand - Google Patents

Verfahren zur herstellung einer thermoplastischen polymervorform sowie ein daraus hergestellter gegenstand

Info

Publication number
EP1082377A1
EP1082377A1 EP99925890A EP99925890A EP1082377A1 EP 1082377 A1 EP1082377 A1 EP 1082377A1 EP 99925890 A EP99925890 A EP 99925890A EP 99925890 A EP99925890 A EP 99925890A EP 1082377 A1 EP1082377 A1 EP 1082377A1
Authority
EP
European Patent Office
Prior art keywords
thermoplastic polymer
container
preform
finish
reheat rate
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.)
Withdrawn
Application number
EP99925890A
Other languages
English (en)
French (fr)
Inventor
David Paul Fischer
Lavonna Suzanne Buehrig
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Chemical Co
Original Assignee
Eastman Chemical Co
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 Chemical Co filed Critical Eastman Chemical Co
Publication of EP1082377A1 publication Critical patent/EP1082377A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/0063After-treatment of articles without altering their shape; Apparatus therefor for changing crystallisation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/07Preforms or parisons characterised by their configuration
    • B29C2949/0715Preforms or parisons characterised by their configuration the preform having one end closed
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/06Injection blow-moulding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/02Thermal after-treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25Solid
    • B29K2105/253Preform
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • B29K2995/0041Crystalline
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2265Oxides; Hydroxides of metals of iron
    • C08K2003/2272Ferric oxide (Fe2O3)

Definitions

  • compositions particularly compositions comprising poly(ethylene terephthalate) or copolymers thereof (hereinafter collectively referred to as "PET"), for example in the form of films, bottles and other containers is well known.
  • PET poly(ethylene terephthalate) or copolymers thereof
  • container- forming compositions in the form of polymer chips or pellets, are usually formed into the container shape in a two stage process. First, a container preform is injection molded; and second, either immediately or after a short storage period, the container preform is blown using compressed air into a mold which is in the final shape of the container.
  • crystallizing a thermoplastic polymer preform is an additional step in the conventional container-forming process.
  • An additional step creates longer and less efficient processing.
  • Several factors effect the rate at which the crystallizing machine can process preforms, including polyester resin properties, oven efficiency, temperature the preform attains in the oven, and time spent in the oven. Accordingly, increasing efficiency by minimizing the amount of time and additional energy required to complete the container-forming process having a crystallization step is still needed.
  • the method of the present invention uses a polymer/reheat rate-increasing additive composition to increase the rate of the polymer crystallization and, thus, the efficiency of a conventional container- forming process.
  • thermoplastic preform a thermoplastic "preform,” “article,” “container” or “bottle” is intended to include the processing of a plurality of thermoplastic preforms, articles, containers or bottles.
  • the rate and percent of crystallization of an amorphous thermoplastic polymer can be increased by incorporating into the polymer a reheat rate-increasing additive before processing by a crystallization machine "Amorphous," for purposes of further defining the polymers of the present invention pnor to crystallization, shall mean substantially noncrystalhne
  • a substantially noncrystalhne polymer typically may have less than about 5 to 7 weight percent crystallinity
  • significant increases in the efficiency of processing heat-set PET container preforms having a crystallized finish portion using the Yoshino process may be obtained by means of the method descnbed herein
  • the present invention is highly useful because 1 ) the method increases the amount of reheat energy which is absorbed by the preforms, and 2) the method increases (nucleates) the spherulitic crystalline growth rate dunng the step of preform/container crystallization Spherulitic crystalline growth may be defined as the increase in spheroid crystalline bodies m the amorphous polymer
  • the method of the present invention provides preforms/containers having a higher or increased degree of crystallinity m a shorter processing time
  • the method of the present invention further provides a container- forming and/or container-processing step having increased output rates.
  • the present invention relates to a method of crystallizing at least a finish portion of a thermoplastic polymer container comprising (i) providing a thermoplastic polymer container comprising a thermoplastic polymer and at least one reheat rate-increasing additive, wherein the container has a finish portion and a body portion; and (ii) exposing at least the finish portion of the container to energy until crystallized.
  • This embodiment differs from that of exposing a preform to energy until crystallized. In this embodiment, at least the fimsh portion of a container, not a preform, is exposed to crystallizing energy
  • the present invention relates to a method of crystallizing a thermoplastic polymer composition
  • the method compnses (l) providing a thermoplastic polymer composition compnsing a thermoplastic polymer and at least one reheat rate-increasing additive, and (n) exposing at least a portion of the composition to energy until crystallized
  • This embodiment is different in that at least a portion of a composition having an additive is exposed to crystallizing energy and not a finish of a preform or a container
  • the thermoplastic polymer composition is in the form of an article, more preferably a container, and even more preferably a bottle
  • the invention relates to a bottle crystallized by the method of this embodiment
  • dicarboxyhc acids to be included with terephthalic acid are: phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, mixtures thereof and the like.
  • the amount of said second dicarboxyhc acid is less than 30 mole% and more preferably less than about 15 mole%.
  • the thermoplastic resin may also contain small amounts of trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, and other polyester forming polyacids or polyols generally known in the art.
  • trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, and other polyester forming polyacids or polyols generally known in the art.
  • the thermoplastic polymers according to this invention include at least one reheat rate-increasing additive.
  • Reheat rate is defined as the change in average temperature of a molded part as a function of exposure to a radiant heat source for a specified time.
  • Suitable reheat rate-increasing additives are well known in the art and include, preferably, black and gray body absorbers such as carbon black, antimony metal, iron oxide and the like, as well as near infrared absorbing dyes, including, but not limited to those disclosed in U.S. 97/15351, which is incorporated herein by reference.
  • the polymer composition may comprise antimony metal in a concentration of at least 10 ppm.
  • the metal if metal is used as the reheat rate-increasing additive, the metal preferably is in particle form for ease of processing.
  • the metal particles are preferably sufficiently fine for them not to be visible to the eye and have a range of sizes such that abso ⁇ tion of radiation occurs over a relatively wide part of the wavelength range and not just at one particular wavelength or over a narrow band.
  • the method of the present invention is particularly suited for use in the production of a heat-set thermoplastic polymer (e.g., polyester) container.
  • a polyester preform for example, is molded in the injection molding machine from a polyester resin containing a reheat rate-increasing additive.
  • the preform is molded according to known techniques, whereby polyester pellets are dried and injection molded to produce clear, amorphous polyester preforms.
  • the amorphous or "glassy" preforms preferably comprise a threaded finish portion and a body portion.
  • the finish portion is crystallized according to the present invention to prevent distortion of the finish upon further processing of the preform to produce a container, or upon heat-filling of the container.
  • the body portion of the preform is typically processed, as by heated blow molding, to form a container having a desired shape and size.
  • crystallization involves exposing at least a portion of the preform finish to radiant heat from lamps in a row of ovens (across a spectrum which may include the IR range) while protecting the body of the preform.
  • the preform is transported to a crystallization machine.
  • the preforms are preferably loaded into carriers which shield the bodies of the preforms against exposure to crystallizing heat, but leave the finishes exposed.
  • the carriers, containing the preforms are passed through the crystallizing machine, where the preform finishes are exposed to infrared energy for a sufficient amount of time to allow the finishes to crystallize.
  • This stage preferably involves exposing at least a portion of the preform finish to radiant heat from lamps in a row of ovens (across a spectrum that may include the IR range) while protecting the body of the preform.
  • the finish is heated to temperatures at which the selected polyester crystallizes rapidly (for PET about 150°C to about 180°C).
  • Crystallization of the finish can be performed either to the preform (as in the Yoshino process), to a pre-bottle (as in the Sidel SRCF process outlined in U.S. Patent No. 5,382,157), or to the actual heat-set bottle.
  • the desired container is preferably blow molded from the preform and heat- set, according to known techniques.
  • the preform body (with or without the crystallized finish) is exposed lamps emitting radiant heat (which may include the IR range of the spectrum) until the preform has reached the appropriate temperature range for bottle blowing (from about 85°C to about 120°C for PET).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP99925890A 1998-05-27 1999-05-27 Verfahren zur herstellung einer thermoplastischen polymervorform sowie ein daraus hergestellter gegenstand Withdrawn EP1082377A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US8692498P 1998-05-27 1998-05-27
US86924P 1998-05-27
PCT/US1999/011659 WO1999061514A1 (en) 1998-05-27 1999-05-27 Method of producing a thermoplastic polymer preform and an article produced therefrom

Publications (1)

Publication Number Publication Date
EP1082377A1 true EP1082377A1 (de) 2001-03-14

Family

ID=22201786

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99925890A Withdrawn EP1082377A1 (de) 1998-05-27 1999-05-27 Verfahren zur herstellung einer thermoplastischen polymervorform sowie ein daraus hergestellter gegenstand

Country Status (7)

Country Link
EP (1) EP1082377A1 (de)
JP (1) JP2002516204A (de)
CN (1) CN1311807A (de)
AR (1) AR018393A1 (de)
BR (1) BR9910709A (de)
CA (1) CA2332984A1 (de)
WO (1) WO1999061514A1 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030031814A1 (en) * 2000-04-28 2003-02-13 Hutchinson Gerald A. Bottles and preforms having a crystalline neck
US7479517B2 (en) * 2003-11-28 2009-01-20 Futura Polyesters Ltd. Process for the preparation of fast reheat (FRH) bottle grade polyethyleneterephthalate (PET) resin
US7358322B2 (en) * 2004-03-09 2008-04-15 Eastman Chemical Company High IV melt phase polyester polymer catalyzed with antimony containing compounds
GB0407114D0 (en) 2004-03-30 2004-05-05 Colormatrix Europe Ltd Polymer additives and methods of use thereof
US7816436B2 (en) * 2004-11-08 2010-10-19 INVISTA North America S.à.r.l. Carbon black with large primary particle size as reheat additive for polyester and polypropylene resins
CN111773762B (zh) * 2020-06-09 2022-03-08 江苏恒科新材料有限公司 一种节能紧凑型聚酯切片结晶干燥系统
WO2023100897A1 (ja) * 2021-11-30 2023-06-08 三菱エンジニアリングプラスチックス株式会社 樹脂組成物、成形品、複合体、および、金属樹脂複合体

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4535118A (en) * 1982-02-24 1985-08-13 The Goodyear Tire & Rubber Company High clarity, low haze polyesters having reduced infrared heat-up times
GB8926631D0 (en) * 1989-11-24 1990-01-17 Ici Plc Polymer compositions
WO1994010242A1 (en) * 1992-10-26 1994-05-11 Allied-Signal Inc. Nucleating system for polyesters and articles formed therefrom

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9961514A1 *

Also Published As

Publication number Publication date
AR018393A1 (es) 2001-11-14
WO1999061514A1 (en) 1999-12-02
CN1311807A (zh) 2001-09-05
BR9910709A (pt) 2001-01-30
JP2002516204A (ja) 2002-06-04
CA2332984A1 (en) 1999-12-02

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