EP1794225A1 - Compositions a base de polymere et de copolymere de polyester contenant des particules de molybdene metalliques - Google Patents

Compositions a base de polymere et de copolymere de polyester contenant des particules de molybdene metalliques

Info

Publication number
EP1794225A1
EP1794225A1 EP05858515A EP05858515A EP1794225A1 EP 1794225 A1 EP1794225 A1 EP 1794225A1 EP 05858515 A EP05858515 A EP 05858515A EP 05858515 A EP05858515 A EP 05858515A EP 1794225 A1 EP1794225 A1 EP 1794225A1
Authority
EP
European Patent Office
Prior art keywords
polyester
particles
polymer
molybdenum particles
metallic molybdenum
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Withdrawn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
EP05858515A
Other languages
German (de)
English (en)
Inventor
Zhiyong Xia
Donna Rice Quillen
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
Priority claimed from US10/996,944 external-priority patent/US20060051542A1/en
Application filed by Eastman Chemical Co filed Critical Eastman Chemical Co
Publication of EP1794225A1 publication Critical patent/EP1794225A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • Metallic molybdenum particles useful according to the invention for the improvement of reheat and color in polyester compositions include those having a range of particle sizes and particle size distributions, although we have found certain particle sizes and relatively narrow particle size distributions to be especially suitable in certain applications.
  • metallic molybdenum particles having a median particle size of approximately 0.15 micrometers ( ⁇ m), and a relatively narrow particle size distribution are advantageous.
  • the size of the metallic molybdenum particles may thus vary within a broad range depending on the method of production, and the numerical values for the particle sizes may vary according to the shape of the particles and the method of measurement.
  • Particle sizes useful according to the invention may be from about 0.005 ⁇ m to about 10 ⁇ m, or from 0.05 ⁇ m to 1 ⁇ m, or from 0.05 ⁇ m to 0.9 ⁇ m.
  • the polyester composition comprises PET, we have found that particle sizes from 0.08 ⁇ m to 1.1 ⁇ m are especially suitable.
  • particle size distributions in which the span (S) is from 0 to 10, or from 0 to 5, or from 0.01 to 2, may be used according to the invention.
  • the amount of metallic molybdenum particles used in the polyester will depend upon the particular application, the desired reduction in reheat time, and the toleration level in the reduction of a* and b* away from zero along with the movement of L* brightness values away from 100.
  • the quantity of metallic molybdenum particles may be at least 1 ppm, or at least 5 ppm, or at least 50 ppm. In many applications, the quantity of metallic molybdenum particles may be at least 50 ppm, in some cases at least 60 ppm, and even at least 70 ppm.
  • proximate the inlet to the esterification reactor may be added at locations including, but not limited to, proximate the inlet to the esterification reactor, proximate the outlet of the esterification reactor, at a point between the inlet and the outlet of the esterification reactor, anywhere along the recirculation loop, proximate the inlet to the prepolymer reactor, proximate the outlet to the prepolymer reactor, at a point between the inlet and the outlet of the prepolymer reactor, proximate the inlet to the polycondensation reactor, or at a point between the inlet and the outlet of the polycondensation reactor.
  • the impact of a reheat additive on the color of the polymer can be judged using a tristimulus color scale, such as the CIE L*a*b* scale.
  • the L* value ranges from 0 to 100 and measures dark to light.
  • the a* value measures red to green with positive values being red and negative values green.
  • the b* value measures yellow to blue with yellow having positive values and blue negative values.
  • polyester polymers include one or more of: PET, polyethylene naphthalate (PEN), poly(1 ,4-cyclo-hexylenedimethylene) terephthalate (PCT), poly( ⁇ thylene-co-1 ,4-cyclohexanedir ⁇ ethylene terephthalate) (PETG), copoly(1 ,4-cyclohexylene dimethylene/ethylene terephthalate) (PCTG) and their blends or their copolymers.
  • the form of the polyester composition is not limited, and includes a melt in the manufacturing process or in the molten state after polymerization, such as may be found in an injection molding machine, and in the form of a liquid, pellets, preforms, and/or bottles.
  • the relative amounts of BHET and oligomeric species will vary depending on whether the process is a direct esterification process, in which case the amount of oligomeric species are significant and even present as the major species, or a transesterification process, in which case the relative quantity of BHET predominates over the oligomeric species.
  • the water is removed as the esterification reaction proceeds and excess ethylene glycol is removed to provide favorable equilibrium conditions.
  • the esterification zone typically produces the monomer and oligomer mixture, if any, continuously in a series of one or more reactors. Alternatively, the monomer and oligomer mixture could be produced in one or more batch reactors.
  • Typical polycondensation catalysts include the compounds of antimony, titanium, germanium, zinc and tin in an amount ranging from 0.1 to 1 ,000 ppm based on the weight of resulting polyester polymer.
  • a common polymerization catalyst added to the prepolymerization zone is an antimony-based polymerization catalyst.
  • Suitable antimony-based catalysts include antimony (III) and antimony (V) compounds recognized in the art, and in particular, diol-soluble antimony (III) and antimony (V) compounds with antimony (III) being most commonly used.
  • Other suitable compounds include those antimony compounds that react with, but are not necessarily soluble in, the diols, with examples of such compounds including antimony (III) oxide.
  • the melt is fed to a peptization zone where it is filtered and extruded into the desired form.
  • the polyester polymers of the present invention are filtered to remove particulates over a designated size, followed by extrusion in the melt phase to form polymer sheets, filaments, or pellets.
  • this zone is termed a "peptization zone,” it is understood that this zone is not limited to solidifying the melt into the shape of pellets, but includes solidification into any desired shape.
  • the polymer melt is extruded immediately after polycondensation. After extrusion, the polymers are quenched, preferably by spraying with water or immersing in a water trough, to promote solidification.
  • the solidified condensation polymers are cut into any desired shape, including pellets.
  • polyester polymer solids whether solid stated or not, are re- melted and re-extruded to form items such as containers (e.g., beverage bottles), filaments, films, or other applications.
  • the pellets are typically fed into an injection molding machine suitable for making preforms which are stretch blow molded into bottles.
  • polyester resin is produced utilizing specific amounts of antimony catalysts, low amounts of phosphorus and a bluing agent which can be a cobalt compound. - 4U -
  • the polyester is produced in a conventional manner as from the reaction of a dicarboxylic acid having from 2 to 40 carbon atoms with polyhydric alcohols such as glycols or diols containing from 2 to about 20 carbon atoms.
  • the dicarboxylic acids can be an alkyl having from 2 to 20 carbon atoms, or an aryl, or alkyl substituted aryl containing from 8 to 16 carbon atoms.
  • An alkyl diester having from 4 to 20 carbon atoms or an alkyl substituted aryl diester having from 10 to 20 carbon atoms can also be utilized.
  • the diols can contain from 2 to 8 carbon atoms and preferably is ethylene glycol.
  • glycol ethers having from 4 to 12 carbon atoms may also be used.
  • polyesters are made from either dimethyl terephthalate or terephthalic acid with ethylene glycol.
  • resin coatings are made, neopentyl glycol is often used in substantial amounts.
  • the molybdenum powder was dispersed in EG (to a final concentration of 4.2 wt.% molybdenum in EG) and then a portion of the dispersion was added to the polymerization process during the prepolymer. Phosphorus was added as a phosphoric acid solution in EG (1 wt.% phosphorus) immediately following the charge.
  • a series of polymers was prepared with molybdenum charges of from 0 ppm (control) to 200 ppm. Using this procedure, polymers were produced with an ItV. of 0.62 dL/g containing 220 ppm antimony as catalyst, 30 ppm phosphorus and 0 to 116 ppm molybdenum. The concentrations of Antimony and phosphorus in the polymer were determined by X-ray fluorescence (XRF), and the final molybdenum concentration in the polymers was determined by ICP-OES.
  • XRF X-ray fluorescence

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention a trait à des compositions à base de polyester comportant des polymères ou des copolymères de polyester incorporant des particules de molybdène métalliques qui améliorent les propriétés de réchauffe des compositions. L'invention a également trait à des procédés pour la fabrication de telles compositions. Les particules de molybdène peuvent être incorporées dans le polyester par compoundage par fusion, ou peuvent être ajoutées à tout stade de polymérisation, telle que lors de la phase de fusion de la polymérisation. Une plage de tailles de particules peut être utilisée, ainsi qu'une plage de granulométries. Les compositions à base de polyester sont aptes à être utilisées dans des emballages obtenus par des procédés dans lesquels une étape de réchauffe est souhaitable.
EP05858515A 2004-09-03 2005-08-29 Compositions a base de polymere et de copolymere de polyester contenant des particules de molybdene metalliques Withdrawn EP1794225A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US93397504A 2004-09-03 2004-09-03
US10/996,944 US20060051542A1 (en) 2004-09-03 2004-11-24 Polyester polymer and copolymer compositions containing metallic molybdenum particles
PCT/US2005/030834 WO2007030090A1 (fr) 2004-09-03 2005-08-29 Compositions a base de polymere et de copolymere de polyester contenant des particules de molybdene metalliques

Publications (1)

Publication Number Publication Date
EP1794225A1 true EP1794225A1 (fr) 2007-06-13

Family

ID=37600947

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05858515A Withdrawn EP1794225A1 (fr) 2004-09-03 2005-08-29 Compositions a base de polymere et de copolymere de polyester contenant des particules de molybdene metalliques

Country Status (7)

Country Link
EP (1) EP1794225A1 (fr)
JP (1) JP2008512560A (fr)
KR (1) KR20070101210A (fr)
AR (1) AR051285A1 (fr)
BR (1) BRPI0514777A (fr)
CA (1) CA2588236A1 (fr)
WO (1) WO2007030090A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015147830A (ja) * 2014-02-05 2015-08-20 帝人株式会社 全脂環族ポリエステルおよびその製造方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8926631D0 (en) * 1989-11-24 1990-01-17 Ici Plc Polymer compositions
JPH10503103A (ja) * 1994-07-25 1998-03-24 アドバンスト・カーディオバスキュラー・システムズ・インコーポレイテッド 潤滑性表面を有する複合体ポリエステル材料
JP2001048972A (ja) * 1999-08-12 2001-02-20 Mitsui Chemicals Inc 中空成形体およびその製造方法
FR2861608B1 (fr) * 2003-10-31 2005-12-23 Commissariat Energie Atomique Dispositif de travail comportant des zones de travail bordees, laboratoire sur puce et microsysteme
GB0407114D0 (en) * 2004-03-30 2004-05-05 Colormatrix Europe Ltd Polymer additives and methods of use thereof
US20060110557A1 (en) * 2004-09-03 2006-05-25 Zhiyong Xia Polyester polymer and copolymer compositions containing metallic tungsten particles
US7662880B2 (en) * 2004-09-03 2010-02-16 Eastman Chemical Company Polyester polymer and copolymer compositions containing metallic nickel particles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007030090A1 *

Also Published As

Publication number Publication date
BRPI0514777A (pt) 2008-06-24
KR20070101210A (ko) 2007-10-16
WO2007030090A1 (fr) 2007-03-15
AR051285A1 (es) 2007-01-03
WO2007030090A9 (fr) 2007-05-10
CA2588236A1 (fr) 2007-03-15
JP2008512560A (ja) 2008-04-24

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