EP0991710A1 - Utilisation de la saccharine pour la stabilisation de polycarbonates thermoplastiques aromatiques - Google Patents

Utilisation de la saccharine pour la stabilisation de polycarbonates thermoplastiques aromatiques

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Publication number
EP0991710A1
EP0991710A1 EP98934928A EP98934928A EP0991710A1 EP 0991710 A1 EP0991710 A1 EP 0991710A1 EP 98934928 A EP98934928 A EP 98934928A EP 98934928 A EP98934928 A EP 98934928A EP 0991710 A1 EP0991710 A1 EP 0991710A1
Authority
EP
European Patent Office
Prior art keywords
weight
hydroxyphenyl
polycarbonate
bis
saccharin
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Withdrawn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
EP98934928A
Other languages
German (de)
English (en)
Inventor
Wolfgang Ebert
Ralf Hufen
Wilfried Haese
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 EP0991710A1 publication Critical patent/EP0991710A1/fr
Withdrawn legal-status Critical Current

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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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
    • G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
    • G11B7/2534—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins polycarbonates [PC]

Definitions

  • thermoplastic, aromatic polycarbonates are thermally stable. If these polycarbonates contain low molecular weight additives containing ester groups, for example mold release agents, then in the melt, for example during extrusion or during injection molding processing, the molecular weight of the aromatic polycarbonate is reduced slightly as a result of transesterification with the additive. This disadvantage is significant in the multiple processing of these additive-containing polycarbonates or in the reuse of old polycarbonate material.
  • thermoplastic polycarbonate still contains traces of alkali, alkaline earth or heavy metal compounds as impurities.
  • the present invention thus relates to the use of saccharin in amounts from 0.001% by weight to 5.0% by weight, preferably from 0.005% by weight to 1.5% by weight, based on 100% by weight.
  • Polycarbonate, for stabilizing thermoplastic, aromatic polycarbonates the still 0.01 wt .-% to 5 wt .-%, preferably 0.05 wt .-% to 3 wt .-%, based on 100 wt .-% %
  • Polycarbonate containing additives containing ester groups.
  • the present invention also includes polycarbonate molding compositions
  • thermoplastic, aromatic polycarbonate in addition B) 0.001% by weight to 5.0% by weight, preferably 0.005% by weight to 1.5% by weight, based on 100% by weight of A, saccharin, and additionally
  • 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.
  • polycarbonates are produced in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents.
  • Diphenols suitable for the production of the polycarbonates are, for example, hydroquinone, res rcin, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers , Bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, ⁇ , ⁇ '-bis (hydroxyphenyl) diisopropylbenzenes, and their ring-alkylated and ring-halogenated compounds.
  • Preferred diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl ) -p-di-isopropylbenzene, 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-
  • diphenols 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-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis- (4th -hydroxyphenyl) -3,3,5-trimethylcyclohexane.
  • Suitable carbonic acid derivatives are, for example, phosgene or diphenyl carbonate.
  • Suitable chain terminators are both monophenols and monocarboxylic acids.
  • Suitable monophenols are phenol itself, alkylphenols such as cresols, p-tert-butylphenol, pn-octylphenol, p-iso-octylphenol, pn-nonylphenol and p-iso- Nonylphenol, halophenols such as p-chlorophenol, 2,4-dichlorophenol, p-bromophenol and 2,4,6-tribromophenol and mixtures thereof.
  • alkylphenols such as cresols, p-tert-butylphenol, pn-octylphenol, p-iso-octylphenol, pn-nonylphenol and p-iso- Nonylphenol, halophenols such as p-chlorophenol, 2,4-dichlorophenol, p-bromophenol and 2,4,6-tribromophenol and mixtures thereof.
  • Suitable monocarboxylic acids are benzoic acid, alkylbenzoic acids and halogenated benzoic acids.
  • Preferred chain terminators are the phenols of the formula (I)
  • R is 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, 1,3,5-tri- (4-hydroxyphenyl) -benzene, l, l, l-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-hydroxyphenyl-isopropyl) phenyl)
  • the amount of branching agents which may be used is 0.05 mol% to 2 mol%, based in turn on moles of diphenols used in each case.
  • 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 polycarbonates to be used according to the invention have average weight-average molecular weights Mw, determined by measuring the relative viscosity in CH 2 C1 2 at 25 ° C. and a concentration of 0.5 g in 100 ml of CH 2 C1 2 between 10,000 and 80,000, preferably between 15,000 and 40,000.
  • Plasticizers and mold release agents as described in the literature and also used for the processing of thermoplastic polycarbonates.
  • the additives according to component C) containing ester groups can be completely esterified compounds or partial esters with unesterified OH groups or unesterified carboxyl groups.
  • the additives according to component C) containing ester groups are composed of aliphatic monoalcohols, aliphatic dialcohols, aliphatic trialcohols, aliphatic tetrols, aliphatic pentols and / or aliphatic hexols with 1 to 15 C atoms, preferably with 2 to 10 C atoms and particularly preferably with 3 to 6 carbon atoms, and aliphatic monocarboxylic acids, aliphatic dicarbon acidic and / or aliphatic T ⁇ carbonsauren with 3 to 34 carbon atoms, preferably 10 to 24 carbon atoms and particularly preferably 12 to 18 carbon atoms
  • the additives containing ester groups have average molecular weights n (number average, determined by end group determination) from 100 to 3000, preferably from 300 to
  • aliphatic alcohols examples include ethanol, propanol, butanol, ethylene glycol, Glyce ⁇ n, pentaerythne, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, hexanol, n-deceyl alcohol, lauryl alcohol, My ⁇ stylglykol, t-amyl alcohol, 1,2,4-
  • aphatic carboxylic acids are butyric acid, isovalenane, capronic, caprylic, capinic, lauinic, myinostin, palmitic, stearic, arachinic, behenic, lignocenic and cerotinic acids, malonic acid, succinic acid, glutaric acid, adipic acid Sebacic acid, dodecanedioic acid and thapsic acid
  • additives according to component C) containing ester groups are ethyl stearate, glycine monostearate, distearate and t ⁇ stearate, butyl laurate, hexyl laurate, pentaerythritol tetra laurate, tetra palmitate, tetra stearate, pentaerythritol t ⁇ laurate , - ⁇ -palmitate and - ⁇ -stearate, sebacic acid monobutyl ester and di-butyl ester and dodecanedioate monobutyl ester and di-butyl ester
  • the additives containing ester groups are known from the literature or can be prepared by processes known from the literature (see, for example, US Pat. No. 3,186,961, JA-Sho-47-41092,
  • Saccharin according to component B) of the molding compositions according to the invention is normal saccharin as it is offered on the world market under the name "Saccharin 550" or "insoluble saccharin” in pharmaceutical quality
  • alkali ions in particular sodium ions
  • Contaminated saccharin that is produced during its production must therefore be purified in a known manner by recrystallization before use according to the invention.
  • DE-OS 3 538 429 discloses a controlled-release powder for use in edible pharmaceutical and other compositions, which is characterized in that the powder contains individual microparticles which contain an active ingredient and, if appropriate, an excipient in intimate mixture with at least one Contain non-toxic polymers (claim 1).
  • the polymer Called polycarbonate (claim 5), as an active ingredient saccharin. (Page 13, lines 36/37 of the DE-OS). Surfactants can be used as excipients (page 18, lines 13 to 33 of DE-OS) (see also the corresponding US Pat. No. 5,354,556).
  • DE-OS 3 743 136 discloses cell and tissue culture substrates which consist of synthetic materials and can contain one or more special compounds.
  • Polycarbonate can also serve as the synthetic material (claim 1 of DE-OS) and saccharin as the special compound (claim 24). This does not affect the use according to the invention.
  • polycarbonates containing UV stabilizers are known, which also contain sulfonimides. Sacchrin can also be used as such. (Column 2, line 16). Mold release agents can also be added (column 3, line 20).
  • the task in the US PS is different.
  • EP-A 0 742 260 (Le A 30 889-EP) saccharin is used to stabilize thermoplastic polycarbonates against the discolouring effect of ⁇ , ⁇ rays. (Page 1 of registration)
  • Components B) and C) can be incorporated into the thermoplastic polycarbonate resins in a known manner either via the melt at temperatures from 200 ° C. to 360 ° C., preferably from 260 ° C. to 320 ° C., or by dissolving the polycarbonates in known inert solvents such as CH 2 C1 2 .
  • melt with the mixed components B) and C) is discharged through the extruder, cooled and granulated.
  • the polycarbonate solutions with the components B) and C) mixed in are concentrated and either cast directly into films, or evaporated and granulated via the extruder or precipitated from the solutions by adding known precipitants such as toluene and isolated as a powder.
  • the polycarbonate molding compositions according to the invention can be processed in a known manner to form any shape, for example by injection molding onto knew machines at temperatures from 200 ° C to 360 ° C. Examples include films, solid sheets, double-wall sheets and compact discs.
  • the present invention thus also relates to the use of the polycarbonate molding compositions according to the invention for the production of films, solid sheets,
  • Double-wall sheets and compact discs Double-wall sheets and compact discs.
  • polycarbonate molding compositions according to the invention can also, before, during or after their processing, other conventional additives, such as, for example, organic phosphites, optionally in combination with monomeric or oligomeric epoxides,
  • Flame retardants in particular fluorine-containing ones, such as polyperfluoroethylene, colorants, pigments, antistatic agents, fillers and reinforcing materials, are added in the customary amounts.
  • polycarbonate molding compositions according to the invention can also be used for mostly non-transparent applications, other thermoplastics in known manner in amounts of 2% by weight to 30% by weight, preferably 5% by weight to 25% by weight and in particular 8% by weight % to 20% by weight, based on 100% by weight of polycarbonate resin.
  • thermoplastics are, for example, aromatic polyester carbonates, polyalkylene terephthalates, EPDM polymers, polystyrene and copolymers and graft copolymers based on styrene, such as in particular ABS.
  • polycarbonate molding compositions according to the invention can be used as moldings wherever thermoplastic polycarbonates have previously been used, i.e. in vehicle construction, in the electrical sector, as safety sheaths, as roof covers in construction, as lamp covers, prisms and in data storage technology. Examples;
  • test platelets were produced by compounding the compositions mentioned on a ZSK 32 twin-screw extruder and then producing the test platelets by injection molding.
  • Test specimen production melt temperature 300 ° C; Mold temperature 90 ° C
  • Saccharin A Na content after atomic absorption: 24 ppm / 27 ppm
  • Saccharin B Na content after atomic absorption: 2 500 ppm / 2 500 ppm polycarbonate: Makrolon 2808 from Bayer AG was used with a
  • Solution viscosity of ( ⁇ re ⁇ ) 1.294 MVR: according to ISO 1133A, at 300 ° C and a weight of 1.2 kg%: percentage by weight in the entire mixture
  • PGG polypropylene glycol with an average molecular weight (weight average) of approx. 2500 As the values show, the solution viscosities and the melt viscosities of the two saccharin-containing compounds differ only slightly within the error limits, although the sodium content is very different.

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  • 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)

Abstract

L'invention concerne l'utilisation de polycarbonates thermoplastiques aromatiques renfermant encore des produits d'addition contenant des groupes esters, les matières moulables, elles-mêmes, de polycarbonates, ainsi que leur utilisation pour la fabrication de différents corps moulés.
EP98934928A 1997-06-20 1998-06-08 Utilisation de la saccharine pour la stabilisation de polycarbonates thermoplastiques aromatiques Withdrawn EP0991710A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19726195A DE19726195A1 (de) 1997-06-20 1997-06-20 Verwendung von Saccharin zur Stabilisierung von thermoplastischen, aromatischen Polycarbonaten
DE19726195 1997-06-20
PCT/EP1998/003425 WO1998058996A1 (fr) 1997-06-20 1998-06-08 Utilisation de la saccharine pour la stabilisation de polycarbonates thermoplastiques aromatiques

Publications (1)

Publication Number Publication Date
EP0991710A1 true EP0991710A1 (fr) 2000-04-12

Family

ID=7833120

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98934928A Withdrawn EP0991710A1 (fr) 1997-06-20 1998-06-08 Utilisation de la saccharine pour la stabilisation de polycarbonates thermoplastiques aromatiques

Country Status (5)

Country Link
US (1) US6350798B1 (fr)
EP (1) EP0991710A1 (fr)
JP (1) JP2002505698A (fr)
DE (1) DE19726195A1 (fr)
WO (1) WO1998058996A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6197854B1 (en) * 2000-04-03 2001-03-06 Bayer Corporation Polycarbonate composition resistant to gamma radiation

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4254015A (en) * 1979-01-22 1981-03-03 The Dow Chemical Company Polycarbonate containing an aromatic sulfonamide as an ignition depressant
IE58110B1 (en) 1984-10-30 1993-07-14 Elan Corp Plc Controlled release powder and process for its preparation
DE3743136A1 (de) 1987-02-17 1988-09-01 Siegel Rolf Zell- und gewebekultursubstrate zur in vitro kultivierung von eukaryontischen zellen
SU1558939A1 (ru) * 1987-06-25 1990-04-23 Научно-производственное объединение "Пластмассы" Термопластична огнестойка полимерна композици
US4782103A (en) * 1987-08-19 1988-11-01 The Dow Chemical Company Ultra violet light resistant carbonate polymers with improved processing stability
JPH0733469B2 (ja) * 1988-05-26 1995-04-12 三菱化学株式会社 ポリカーボネート樹脂組成物
JPH0225558A (ja) * 1988-07-13 1990-01-29 Kanmeta Eng Kk 溶射方法
US5210124A (en) * 1989-12-28 1993-05-11 General Electric Company Tri or tetraesters of aliphatic monocarboxylic acids of 6 to 9 carbon atoms and pentaerythritol as mold releases for aromatic polycarbonates
DE19516787A1 (de) * 1995-05-08 1996-11-14 Bayer Ag Gegen Gamma-Strahlung stabilisierte (Co)Polycarbonate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9858996A1 *

Also Published As

Publication number Publication date
US6350798B1 (en) 2002-02-26
WO1998058996A1 (fr) 1998-12-30
DE19726195A1 (de) 1998-12-24
JP2002505698A (ja) 2002-02-19

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