EP1141129A1 - Polycarbonates contenant de l'iode et/ou du brome utilises pour des pieces moulees a fort pouvoir de contraste et pieces moulees produites avec ces polycarbonates - Google Patents

Polycarbonates contenant de l'iode et/ou du brome utilises pour des pieces moulees a fort pouvoir de contraste et pieces moulees produites avec ces polycarbonates

Info

Publication number
EP1141129A1
EP1141129A1 EP99963402A EP99963402A EP1141129A1 EP 1141129 A1 EP1141129 A1 EP 1141129A1 EP 99963402 A EP99963402 A EP 99963402A EP 99963402 A EP99963402 A EP 99963402A EP 1141129 A1 EP1141129 A1 EP 1141129A1
Authority
EP
European Patent Office
Prior art keywords
weight
iodine
brominated
polycarbonates
ray contrast
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Withdrawn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
EP99963402A
Other languages
German (de)
English (en)
Inventor
Martin Döbler
Siegfried Neumann
Axel Brenner
Walter Köhler
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.)
Bayer AG
Original Assignee
Bayer AG
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 Bayer AG filed Critical Bayer AG
Publication of EP1141129A1 publication Critical patent/EP1141129A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
    • C08G64/10—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B90/00—Instruments, implements or accessories specially adapted for surgery or diagnosis and not covered by any of the groups A61B1/00 - A61B50/00, e.g. for luxation treatment or for protecting wound edges
    • A61B90/39—Markers, e.g. radio-opaque or breast lesions markers
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63H—TOYS, e.g. TOPS, DOLLS, HOOPS OR BUILDING BLOCKS
    • A63H33/00—Other toys
    • A63H33/001—Toy-moulding appliances; Toy moulding

Definitions

  • the invention relates to the use of iodine and / or bromine-containing thermoplastics for molded parts with high X-ray contrast and those produced therewith
  • Molded parts especially toys and medical devices.
  • Such molding materials can be made radiopaque by suitable additives.
  • X-ray detectable plastic molding compositions have also been described in Silberman-Hazony, Encycl. Polym. Be. Closely. (1988), 14, 1-8. Thermoplastics with various heavy metals have been described as X-ray contrast media. A halogen-containing terpolymer was also mentioned.
  • FR 2223403 describes PVC and other vinyl polymers with iodine-containing salicylic acids, benzoic acids and their esters, which are similar to those of US Pat. Nos. 3,361,700 and 3,645,955.
  • PVC is not suitable for applications where high transparency and good mechanical properties are required.
  • transparent plastic molding compositions made of polycarbonates with iodine-containing end groups have also been described. In this way, iodine is only introduced at the end groups. All other monomers remain unmodified, which is why the weight fraction of iodine remains limited.
  • the layer thickness at which the plastic can still be recognized should be as small as possible, but at most 1.2 mm.
  • the task was to develop molding compounds with good mechanics and
  • Transparency have sufficient contrast in X-ray examinations.
  • the addition of heavy metals should be avoided for toxicological reasons, since materials for children's toys were sought.
  • the subject of the present application is accordingly the use of iodine and / or bromine-containing transparent thermoplastics for molded parts with high X-ray contrast.
  • Polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds which contain bromine or iodine are suitable.
  • Particularly suitable plastics are polycarbonates or copolycarbonates based on diphenols.
  • oligomers according to the invention can, however, also be used with poly- or copolyacrylates and poly- or copolymer-methacrylates such as, for example, brominated and / or iodinated poly- or copolymethyl methacrylate, but also as copolymers with styrene, such as transparent brominated and / or iodinated polyurethane-acrylonitrile
  • SAN can be used.
  • poly- or copolycondensates of terephthalic acid e.g. Poly- or copolyethylene terephthalate (PET or CoPET) or glycol-modified PET (PETG) can be mixed in.
  • PET or CoPET Poly- or copolyethylene terephthalate
  • PETG glycol-modified PET
  • Brominated and / or iodinated polycarbonates are particularly preferred for moldings with high X-ray contrast, the polycarbonates having an iodine and / or brominated diol unit and a weight average molecular weight Mw
  • polycarbonates which, as a diol unit, between 0.1 and 100% by weight, preferably between 1 and 100% by weight, particularly preferably between 10 and 100% by weight, preferably 100% by weight, of brominated and / or iodinated 2,2-bis - (4-hydroxyphenyl) propane included.
  • diols are 2,2-bis
  • the molded parts can consist entirely of the iodine and / or bromine-containing polycarbonate.
  • the iodine and / or bromine content in the molded part is then between 0.2 to
  • the moldings then contain the iodine and / or bromine-containing polycarbonates in amounts between 0.1 to 100% by weight, preferably 1 to 30% by weight, particularly preferably 2 to 20% by weight and very particularly preferably 2 to 10 % By weight based on the molded part.
  • the molded parts can optionally additionally contain at least one transparent thermoplastic, preferably a non-halogenated polycarbonate or copolycarbonate in amounts of 70 to 99% by weight, preferably 80 to 98% by weight, particularly preferably 90 to 98% by weight, based on the molded part his.
  • at least one transparent thermoplastic preferably a non-halogenated polycarbonate or copolycarbonate in amounts of 70 to 99% by weight, preferably 80 to 98% by weight, particularly preferably 90 to 98% by weight, based on the molded part his.
  • the polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds are particularly preferably used as transparent thermoplastics.
  • Particularly suitable transparent thermoplastics are polycarbonates or copolycarbonates based on diphenols.
  • the oligomers according to the invention can also be mixed with poly- or copolyacrylates and poly- or copolymethacrylates such as e.g. Poly- or copolymethyl methacrylate, but also as copolymers with styrene such as transparent polystyrene acrylonitrile (SAN) can be used.
  • SAN transparent polystyrene acrylonitrile
  • PET or CoPET poly or copolyethylene terephthalate
  • PETG glycol-modified PET
  • Thermoplastic, aromatic polycarbonates in the sense of the present invention are both homopolycarbonates and copolycarbonates; the polycarbonates can be linear or branched in a known manner.
  • Carbonic acid derivatives optionally chain terminators and optionally branching agents.
  • Diphenols suitable for the preparation of the polycarbonates are, for example, hydroquinone, resorcinol, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, Bis- (hydroxyphenyl) ketones, bis- (hydroxyphenyl) sulfones, bis- (hydroxyphenyl) sulfoxides, ä, ä'-bis- (hydroxyphenyl) diisopropylbenzenes, and their alkylated compounds.
  • the iodinated and / or brominated derivatives of these diols are suitable for the preparation of the polycarbonates and / or copolycarbonates according to the invention.
  • Preferred for the polycarbonates and / or copolycarbonates according to the invention are tetrabromobisphenol and / or tetraiodobisphenol, optionally in a mixture with one another or optionally with other diols.
  • a preferred copolymer for the polycarbonates and / or copolycarbonates according to the invention is one of tetrabromobisphenol with bisphenol A as a comonomer.
  • a preferred mixture for the polycarbonates and / or copolycarbonates according to the invention is a mixture of polymers from tetrabromobisphenol with polymers with bisphenol A.
  • Preferred diphenols for the additional polycarbonates and / or copolycarbonates are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) - propane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) ) sulfone, 2,4-bis- (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene,
  • Particularly preferred diphenols for the additional polycarbonates and or copolycarbonates are 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2 , 2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hj-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl ) -cyclohexane and l, l-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
  • Suitable carbonic acid derivatives are, for example, phosgene or diphenyl carbonate.
  • Suitable chain terminators for the iodine and / or bromine-containing polycarbonates according to the invention, but also the additional polycarbonates and / or copolycarbonates are both monophenols and monocarboxylic acids.
  • Suitable monophenols are phenol itself, alkylphenols such as cresols, p-tert-butylphenol, p-n-octylphenol, p-iso-
  • halophenols such as p-chlorophenol, 2,4-dichlorophenol, p-bromophenol and 2,4,6-tribromophenol, especially 2,4,6-triiodophenol, p- Jodpbenol, as well as their mixtures.
  • the preferred chain terminator is p-tert-butylphenol.
  • Suitable monocarboxylic acids are benzoic acid, alkylbenzoic acids and halogenated benzoic acids.
  • Preferred chain terminators are the phenols of the formula (I)
  • R is hydrogen, tert-butyl or a branched or unbranched C 8 and / or C 9 alkyl radical.
  • the amount of chain terminator to be used is 0.1 mol% to 5 mol%, based on moles of diphenols used in each case.
  • the chain terminators can be added before, during or after phosgenation.
  • Suitable branching agents are the tri- or more than trifunctional compounds known in polycarbonate chemistry, in particular those with three or more than three phenolic OH groups.
  • Suitable branching agents are, for example, phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl ) -heptane, l, 3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2- Bis- [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenyl isopropyl) phenol, 2,6-bis (2-hydroxy-5 '-methyl-benzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, hexa- (4- (4-hydroxyphenylisopropyl) phenyl) -orthotere
  • the amount of the branching agents to be used is from 0.05 mol% to
  • the branching agents can either be introduced with the diphenols and the chain terminators in the aqueous alkaline phase, or added dissolved in an organic solvent before the phosgenation. In the case of the transesterification process, the branching agents are used together with the diphenols.
  • thermoplastic polycarbonates All of these measures for producing the thermoplastic polycarbonates are familiar to the person skilled in the art.
  • the additional polycarbonates and / or copolycarbonates can be present in amounts between 0 and 99.9% by weight, preferably 70 and 99% by weight, particularly preferably between 80 and 98% by weight and very particularly preferably between 90 and 98% by weight. -% based on the molded part.
  • thermoplastics preferably poly- and copolycarbonates, such as e.g. Stabilizers (as described, for example, in EP 0 839 623 AI or EP 0 500 496 AI), in particular thermal stabilizers, in particular organic phosphites or phosphines, mold release agents, for example fatty acid esters of glycerol or tetramethanol methane, where unsaturated fatty acid can also be completely or partially epoxidized, in particular Glycerol monostearate or pentaerytetratetearate (PETS), flame retardants, antistatic agents, UV absorbers, for example triazoles, fillers, foaming agents, dyes, pigments, optical brighteners, and nucleating agents or the like, preferably in amounts of up to 5% by weight, preferably 0.01 up to 5% by weight based on the entire mixture, particularly preferably 0.01% by weight to 1% by weight based on the
  • transesterification catalysts known from the literature such as organic tin or titanium compounds, can also optionally be used in the amounts known from the literature, preferably between 10 and
  • UV stabilizers from the triazole series.
  • the x-ray-opaque polymer compositions thus obtained can be prepared by the usual methods, e.g. Hot pressing, spinning, extruding or injection molding, can be converted into shaped objects, e.g. Toy parts, but also fibers,
  • the polymer compositions can also be processed into cast films.
  • the invention therefore further relates to the use of the polymer compositions according to the invention for the production of a shaped article.
  • the use of multilayer systems is also of interest.
  • the invention is also of interest.
  • Polymer composition with a relatively high content of bromine- or iodine-containing additives in a thin layer applied to a molded article made of a polymer which is transparent to X-rays The application can take place at the same time or immediately afterwards with the shaping of the base body, for example by coextrusion or multi-component injection molding. However, it can also be applied to the finished molded body, for example by lamination with a film or by coating with a solution.
  • the molding compounds are particularly suitable for transparent children's toy parts or for medical applications. Such molded parts are particularly suitable for small parts of children's toys. Examples:

Abstract

L'invention concerne des matières thermoplastiques contenant de l'iode et/ou du brome utilisées pour des pièces moulées à haut pouvoir de constraste. L'invention concerne également les pièces moulées ainsi produites, notamment des jouets et des appareils médicaux.
EP99963402A 1998-12-18 1999-12-07 Polycarbonates contenant de l'iode et/ou du brome utilises pour des pieces moulees a fort pouvoir de contraste et pieces moulees produites avec ces polycarbonates Withdrawn EP1141129A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19858788 1998-12-18
DE19858788 1998-12-18
PCT/EP1999/009556 WO2000037562A1 (fr) 1998-12-18 1999-12-07 Polycarbonates contenant de l'iode et/ou du brome utilises pour des pieces moulees a fort pouvoir de contraste et pieces moulees produites avec ces polycarbonates

Publications (1)

Publication Number Publication Date
EP1141129A1 true EP1141129A1 (fr) 2001-10-10

Family

ID=7891783

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99963402A Withdrawn EP1141129A1 (fr) 1998-12-18 1999-12-07 Polycarbonates contenant de l'iode et/ou du brome utilises pour des pieces moulees a fort pouvoir de contraste et pieces moulees produites avec ces polycarbonates

Country Status (6)

Country Link
EP (1) EP1141129A1 (fr)
JP (1) JP2002533515A (fr)
CN (1) CN1330688A (fr)
AU (1) AU1971300A (fr)
CA (1) CA2355142A1 (fr)
WO (1) WO2000037562A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020173665A1 (fr) 2019-02-28 2020-09-03 Speed Care Mineral Gmbh Pâte pour le marquage de structures textiles et/ou d'autres produits sans pouvoir de contraste

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005325319A (ja) * 2004-04-15 2005-11-24 Teijin Chem Ltd ポリカーボネート樹脂組成物
CA2577018C (fr) * 2004-08-13 2012-03-27 Reva Medical, Inc. Polymeres bioresorbables intrinsequement radio-opaques pour usages multiples
JP5347244B2 (ja) * 2006-08-04 2013-11-20 三菱化学株式会社 ハロゲン含有ポリカーボネート樹脂の製造方法
WO2016103224A2 (fr) * 2014-12-23 2016-06-30 Rutgers, The State University Of New Jersey Monomères et polymères de diphénol iodés biocompatibles

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Publication number Priority date Publication date Assignee Title
US4182787A (en) * 1978-06-19 1980-01-08 General Electric Company Optically transparent, radiographically opaque tubing
DE68913633T2 (de) * 1988-09-06 1994-06-09 Mitsubishi Chem Ind Medizinische Formkörper und Verfahren zu ihrer Herstellung.
JPH0641416A (ja) * 1992-07-24 1994-02-15 Nippon Steel Chem Co Ltd 難燃性ポリカーボネート樹脂組成物およびその成形品
DE4229642A1 (de) * 1992-09-04 1994-03-10 Bayer Ag Pulvermischungen für matte Polycarbonat-Formmassen
JPH0857033A (ja) * 1994-08-25 1996-03-05 Terumo Corp Ｘ線造影性医療用成型品
DE19726191A1 (de) * 1997-06-20 1998-12-24 Bayer Ag Verwendung von Jod-phenyl-carbonat-haltigen Polycarbonaten zur Herstellung von speziellen Formteilen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0037562A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020173665A1 (fr) 2019-02-28 2020-09-03 Speed Care Mineral Gmbh Pâte pour le marquage de structures textiles et/ou d'autres produits sans pouvoir de contraste

Also Published As

Publication number Publication date
JP2002533515A (ja) 2002-10-08
AU1971300A (en) 2000-07-12
CN1330688A (zh) 2002-01-09
CA2355142A1 (fr) 2000-06-29
WO2000037562A1 (fr) 2000-06-29

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